Coloring composition, cured film, color filter, method for producing color filter, solid-state imaging element, and image display device

ABSTRACT

Provided are a coloring composition having improved heat resistance; and a cured film, a color filter, a method for producing a color filter, and a solid-state imaging element and an image display device, each of which uses the coloring composition. The coloring composition includes a dye (A) represented by the following General Formula (I) and a polymerizable compound (B). General Formula (I) is (R) m -Q-(D) n , wherein Q represents an (m+n)-valent linking group, R represents a substituent, D represents a dye residue, m represents an integer of 0 to 6, n represents an integer of 2 to 8, and (m+n) represents an integer of 2 to 8. In the case where m is 2 or more, a plurality of R&#39;s may be different from each other, and in the case where n is 2 or more, a plurality of D&#39;s may be different from each other.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation of PCT International Application No. PCT/JP2014/06 8023 filed on Jul. 7, 2014, which claims priority under 35 U.S.C § 119(a) to Japanese Patent Application No. 2013-143366 filed on Jul. 9, 2013 and Japanese Patent Application No. 2014-073225 filed on Mar. 31, 2014. Each of the above application(s) is hereby expressly incorporated by reference, in its entirety, into the present application.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a coloring composition which is suitable for production of a color filter used for a liquid crystal display element, a solid-state imaging element, or the like, a cured film, a color filter, a method for producing a color filter, a solid-state imaging element, and an image display device.

2. Description of the Related Art

As one of the methods for producing a color filter which is used for a liquid crystal display device, a solid-state imaging element, or the like, there is a pigment dispersion method. As the pigment dispersion method, there is a method for producing a color filter by photolithography using a coloring photosensitive composition which is obtained by dispersing pigments in various photosensitive compositions (JP2005-316012A, JP3309514B (JP-H06-208021A), and JP2006-258916A). That is, a coloring photosensitive composition is applied onto a substrate by using a spin coater, a roll coater, or the like, the substrate is dried to form a coating film, and the coating film is developed by pattern exposure, thereby obtaining colored pixels. This operation is repeated for the number of the desired hues to manufacture a color filter.

The method is stable with respect to light or heat due to a use of pigments, and positional accuracy is sufficiently secured since patterning is performed by photolithography. Accordingly, the method has been widely used as a method suitable for producing a color filter for color display or the like.

Meanwhile, in recent years, there has been a demand for a color filter for a solid-state imaging element such as a CCD to have enhanced definition. As the definition of the color filter is heightened, the pattern size tends to be decreased, but it is considered that the pigment dispersion method which has been widely used in the related art has difficulty in further improving resolution while also decreasing the pattern size. One of the reasons therefor is that coarse particles generated due to the aggregation of pigment particles cause color unevenness in a fine pattern. Accordingly, the pigment dispersion method which has been widely used so far has been in a recent situation where it has not necessarily been appropriately used for purposes requiring a fine pattern, such as in a solid-state imaging element.

In the related art, a color filter has been manufactured using a pigment as a coloring agent, but use of a dye instead of a pigment is under examination. In the case of using the dye, the points shown below particularly become problems.

(1) A dye is generally inferior to a pigment in terms of light fastness and heat resistance. In particular, there is a problem in that optical characteristics are changed due to a high-temperature process performed at the time when a film is formed of indium tin oxide (ITO) which is widely used as an electrode of a liquid crystal display or the like.

(2) Since a dye tends to inhibit a radical polymerization reaction, there is difficulty in designing a coloring photosensitive composition in a system using radical polymerization as curing means.

Particularly, in the case where photolithography is used for the manufacture of a color filter, the following points become problems.

(3) Since an ordinary dye exhibits low solubility in an aqueous alkaline solution or an organic solvent (hereinafter simply referred to as a solvent), it is difficult to obtain a coloring photosensitive composition having a desired spectrum.

(4) A dye interacts with other components in a coloring photosensitive composition in many cases, and thus, it is difficult to regulate the solubility (developability) of exposed and unexposed areas.

(5) In the case where the molar absorption coefficient (c) of a dye is low, it is necessary to add the dye in a large amount. As a result, amounts of other components in a coloring photosensitive composition, such as a polymerizable compound, and a photopolymerization initiator, have to be relatively reduced, and curability of the composition as well as heat resistance, developability, and the like of the cured composition deteriorate.

Due to these problems, it has been difficult so far to form a colored pattern which is constituted with a fine and thin film for a high-definition color filter and has excellent fastness by using a dye. Further, in the case of a color filter for a solid-state imaging element, a colored layer is required to be formed of a thin film of 1 μm or less. Accordingly, in order to obtain desired absorption, a large amount of a dye needs to be added to a curable composition, and as a result, the aforementioned problems arise.

Furthermore, for a coloring photosensitive composition including a dye, it is pointed out that in the case where a heating treatment is carried out after forming a film, a phenomenon of color migration easily occurs between colored patterns with different hues adjacent to each other or between layers stacked and disposed on each other. In addition to color migration, there are also problems in that a pattern is easily peeled off in an area with a low exposure dose due to decrease in sensitivity; since the amount of photosensitive components contributing to photolithographic properties is relatively reduced, an intended shape or color density cannot be obtained due to heat sagging or elution caused at the time of development; and the like.

As methods for solving such problems, methods for resolving the problems by polymerizing a dye have been suggested (for example, JP2012-32754A, JP2007-138051A, JP3736221B (JP2000-162429A), and JP2003-246935A).

SUMMARY OF THE INVENTION

However, a method for obtaining a dye polymer by the related art includes subjecting a dye having a polymerizable group alone to a polymerization reaction, and a deviation in the molecular weight or composition of the obtained dye easily occurs. Thus, in the related art, dyes may sometimes be decomposed in an excessive heating process.

The present invention has been made, taking this situation into consideration, and has an object to provide a coloring composition having excellent heat resistance, a cured film, a color filter, a method for producing a color filter, a solid-state imaging element, and an image display device.

The present inventors have conducted extensive studies, and as a result, they have found that it is possible to obtain a coloring composition having excellent heat resistance, using a coloring composition in which a dye residue contains 2 to 8 dyes, thereby completing the present invention.

Specifically, the problems were solved by the following means <1>, and preferably <2> to <17>.

<1> A coloring composition including a dye (A) represented by the following General Formula (I) and a polymerizable compound (B): (R)_(m)-Q-(D)_(n)  General Formula (I)

(in General Formula (I), Q represents an (m+n)-valent linking group, R represents a substituent, D represents a dye residue, m represents an integer of 0 to 6, n represents an integer of 2 to 8, and (m+n) represents an integer of 2 to 8; in the case where m is 2 or more, a plurality of R's may be different from each other; and in the case where n is 2 or more, a plurality of D's may be different from each other).

<2> The coloring composition as described in <1>, in which at least one selected from the linking group Q, the substituent R, and the dye residue D in General Formula (I) contains an acid group.

<3> The coloring composition as described in <1> or <2>, in which the dye residue D in General Formula (I) is constituted with a cationic site and a counter anion.

<4> The coloring composition as described in <1> or <2>, in which the dye residue D in General Formula (I) has a cationic site and an anionic site in a molecule thereof.

<5> The coloring composition as described in any one of <1> to <4>, in which the cationic site constituting the dye residue D in General Formula (I) is selected from a dipyrromethene dye, a triarylmethane dye, a xanthene dye, a cyanine dye, and a squarylium dye.

<6> The coloring composition as described in <3>, in which the counter anion constituting the dye residue D in General Formula (I) is selected from a sulfonic acid anion, a sulfonylimide anion, a bis(alkylsulfonyl)imide anion, a tris(alkylsulfonyl)methide anion, a carboxylic acid anion, a tetraarylborate anion, BF₄ ⁻, PF₆ ⁻, and SbF₆ ⁻.

<7> The coloring composition as described in any one of <1> to <6>, in which at least one of the substituents R in General Formula (I) is an acid group.

<8> The coloring composition as described in any one of <1> to <7>, further including a pigment (C) other than the dye (A).

<9> The coloring composition as described in any one of <1> to <8>, further including a photopolymerization initiator (D).

<10> The coloring composition as described in <9>, in which the photopolymerization initiator (D) is an oxime compound.

<11> The coloring composition as described in any one of <1> to <10>, which is used for forming a colored layer of a color filter.

<12> The coloring composition as described in any one of <1> to <11>, in which the dye represented by General Formula (I) is an organic solvent-soluble dye.

<13> The coloring composition as described in any one of <1> to <12>, in which the dye represented by General Formula (I) has a polymerizable group.

<13-1> The coloring composition as described in any one of <1> to <12>, in which at least one of the substituents R in General Formula (I) is a polymerizable group.

<14> The coloring composition as described in any one of <1> to <13>, in which the molecular weight of the dye represented by General Formula (I) is 2000 to 6000.

<15> A cured film obtained by curing the coloring composition as described in any one of <1> to <14>.

<16> A color filter obtained by using the coloring composition as described in any one of <1> to <14>.

<17> A method for producing a color filter, including a step of applying the coloring composition as described in any one of <1> to <14> onto a support to form a coloring composition layer, a step of patternwise exposing the coloring composition layer, and a step of removing an unexposed area by development to form a colored pattern.

<18> A method for producing a color filter, including a step of applying the coloring composition as described in any one of <1> to <14> onto a support to form a coloring composition layer, and curing the coloring composition layer to form the colored layer, a step of forming a photoresist layer on the colored layer, a step of patterning the photoresist layer by exposure and development to obtain a resist pattern, and a step of dry-etching the colored layer using the resist pattern as an etching mask to form a colored pattern.

<19> A solid-state imaging element or an image display device, including the color filter as described in <16> or a color filter produced by the method for producing a color filter as described in <17> or <18>.

According to the present invention, it became possible to provide a coloring composition having improved heat resistance.

Furthermore, according to the present invention, it also became possible to provide a cured film, a color filter, a method for producing a color filter, a solid-state imaging element, and an image display device, each of which uses such a coloring composition.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Hereinafter, the coloring composition, the cured film, the pattern forming method, the method for producing a color filter, the solid-state imaging element, and the image display device of the present invention will be described in detail.

The explanation of constituents in the present invention described below will be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

In citations for a group (atomic group) in the present specification, when the group is denoted without specifying whether it is substituted or unsubstituted, the group includes both a group having no substituent and a group having a substituent. For example, an “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group), but also an alkyl group having a substituent (substituted alkyl group).

Furthermore, “actinic ray(s)” or “radiation” in the present specification means, for example, a bright line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV rays), X-rays, electron beams, or the like. In addition, in the present invention, light means actinic rays or radiation. “Exposure” in the present specification includes, unless otherwise specified, not only exposure by a mercury lamp, far ultraviolet rays represented by an excimer laser, X-rays, EUV rays, or the like, but also writing by particle rays such as electron beams and ion beams.

In the present specification, a numeral value range represented by “(a value) to ˜(a value)” means a range including the numeral values represented before and after “(a value) to (a value)” as a lower limit value and an upper limit value, respectively.

In the present specification, the total solid content refers to a total mass of the components remaining when a solvent is excluded from the entire composition of a coloring composition.

Furthermore, in the present specification, “(meth)acrylate” represents either or both of an acrylate and a methacrylate, “(meth)acryl” represents either or both of an acryl and a methacryl, and “(meth)acryloyl” represents either or both of an acryloyl and a methacryloyl.

In addition, in the present specification, a “monomer material” and a “monomer” have the same definition. The monomer in the present specification refers to a compound which is distinguished from an oligomer or a polymer and has a weight-average molecular weight of 2,000 or less. In the present specification, a polymerizable compound refers to a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group involved in a polymerization reaction.

In the present specification, a term “step” includes not only an independent step, but also steps which are not clearly distinguished from other steps if an intended action of the steps is obtained.

Coloring Composition

The coloring composition of the present invention includes a dye (A) represented by the following General Formula (I) and a polymerizable compound (B). (R)_(m)-Q-(D)_(n)  General Formula (I)

(In General Formula (I), Q represents an (m+n)-valent linking group, R represents a substituent, and D represents a dye residue. m represents an integer of 0 to 6, n represents an integer of 2 to 8, and (m+n) represents an integer of 2 to 8. In the case where m is 2 or more, a plurality of R's may be different from each other, and in the case where n is 2 or more, a plurality of D's may be different from each other.)

By adopting the above configuration, the present invention can solve the problems as shown below. Incidentally, it is needless to say that it is not a precondition of the coloring composition of the present invention to solve all of the problems below.

In a first aspect, it is possible to provide a coloring composition, in which decomposition of a dye is inhibited even in an excessive heating process (heat resistance is provided), and further, color migration to another pattern is inhibited.

In a second aspect, it is possible to provide a coloring composition, in which a colored pattern having improvement in pattern deficit or excellent in pattern linearity can be formed even when a fine pattern is formed by photolithography.

In as third aspect, it is possible to provide a coloring composition, in which a colored pattern excellent in resistance to a developing liquid and a peeling solution of a photoresist can be formed even when a pattern is formed by a dry etching method.

In a fourth aspect, it is possible to provide a cured film having excellent color characteristics, and a color filter including the cured film.

In a fifth aspect, it is possible to provide a pattern forming method by which a colored pattern having excellent color characteristics can be formed, and a method for producing a color filter.

In a sixth aspect, it is possible to provide a solid-state imaging element and an image display device (a liquid crystal display device, an organic EL display device, and the like), each of which includes a color filter having excellent color characteristics.

Although the action mechanism for accomplishing the tasks are still not clear, by linking a plurality of dye residues, the heat resistance is improved and excessive aggregation of the dye residues is inhibited. Thus, it is presumed that one of the reasons therefor is the evenness of penetration of a curing and developing liquid.

Moreover, since the dye (A) has a small deviation in the molecular weight unlike a case of dye multimers (polymers) in the related art, it becomes easier to solve the problems as described above. Such problems are easily caused with dyes, but even in the case of using pigments, particularly, in the case of using pigments having performance close to that of the dyes, the present invention can preferably employ them.

In the coloring composition of the present invention (hereinafter simply referred to as “the composition of the present invention” in some cases), the polymerizable compound (B) is appropriately selected in accordance with uses or production methods. In addition, it is preferable that the coloring composition of the present invention further includes a pigment (C) or a photopolymerization initiator (D), in addition to the dye (A).

For example, in the case of forming a colored layer by a photoresist, the coloring composition of the present invention is preferably a composition including a dye (A), a polymerizable compound (B), a pigment (C), a photopolymerization initiator (D), and an alkali-soluble resin (F).

In addition, in the case of forming a colored layer by dry etching, the composition including the dye (A), the polymerizable compound (B), the pigment (C), and the photopolymerization initiator (D) of the present invention is preferable. Further, the composition may further include components such as a surfactant and a solvent.

One kind or two or more kinds of each of these components may be included.

Hereinafter, the components included in the coloring composition of the present invention will be described in detail.

<Dye (A) Represented by General Formula (I)>

The composition of the present invention contains at least one kind of dye represented by the following General Formula (I) (hereinafter simply referred to as a “dye (A)” in some cases).

More specifically, the dye (A) is an oligomer having a partial structure, which has a colorant skeleton of which a maximum absorption wavelength is present in a range of 400 nm to 780 nm, in a molecular structure thereof, and includes the structure ranging from a dimer to an octamer. In the coloring composition of the present invention, the dye (A) functions as, for example, a coloring agent. (R)_(m)-Q-(D)_(n)  General Formula (I)

(In General Formula (I), Q represents an (m+n)-valent linking group, R represents a substituent, and D represents a dye residue. m represents an integer of 0 to 6, n represents an integer of 2 to 8, and (m+n) represents an integer of 2 to 8. In the case where m is 2 or more, a plurality of R's may be different from each other, and in the case where n is 2 or more, a plurality of D's may be different from each other.)

It is preferable that at least one selected from the linking group Q, the substituent R, and the dye residue D in General Formula (I) contains an acid group.

Q in General Formula (I) represents an (m+n)-valent linking group, and is preferably a tri- to hexa-valent linking group.

The mass of a moiety represented by Q in one molecule of the dye represented by General Formula (I) is preferably 50 to 2000, more preferably 200 to 1000, and still more preferably 250 to 600.

The (m+n)-valent linking group represented by Q is preferably a linking group represented by the following General Formula (Q-1) or (Q-2).

(In General Formula (Q-1), R¹ to R⁴ each independently represent a linking group or a substituent, provided that at least two of R¹ to R⁴ are linking groups.)

The substituents represented by R¹ to R⁴ are each an alkyl group having 1 to 10 carbon atoms (preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms), an aryl group having 6 to 20 carbon atoms (preferably an aryl group having 6 to 14 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms), more preferably an alkyl group having 1 to 10 carbon atoms, and still more preferably a methyl group, an ethyl group, or a propyl group.

The linking groups represented by R¹ to R⁴ are each an alkylene group (preferably a linear or branched alkylene group, more preferably —(CH₂)_(n1)— (in which n1 is preferably an integer of 1 to 3)), —O—, —CO—, —SO₂—, or —NRa— (provided that Ra is an alkyl group having 1 to 5 carbon atoms or a hydrogen atom), with a group formed by combination of two or more of these groups being more preferable, and a group formed by combination of two or more of an alkylene group, —O—, —CO—, and —NRa-being even more preferable.

The number of atoms for linking R or D with C in the center of the linking groups represented by R¹ to R⁴ is each preferably 1 to 15, and each more preferably 1 to 10. For example, in the case where the linking group is —CH₂—CH₂—C(═O)—O—CH₂—, the number of atoms for linking R or D with C in the center is 5.

(In General Formula (Q-2), A¹ to A⁴ each independently represent a carbon atom or a nitrogen atom. R¹¹ to R¹⁶ each independently represent a hydrogen atom, ═O, or a linking group. The dotted line represents a single bond or a double bond.)

Examples of the 6-membered ring including A¹ to A⁴ in General Formula (Q-2) include an aliphatic ring, a heterocycle, and a benzene ring, among which the heterocycle and the benzene ring are preferable.

The linking groups represented by R¹¹ to R¹⁶ each have the same definitions as those of the linking groups represented by R¹ to R⁴ in General Formula (Q-1), and preferred ranges thereof are also the same.

Specific examples of the (m+n)-valent linking group represented by Q are shown below, but the present invention is not limited thereto.

Among these, (1), (7), (10), (13) to (16), (18), (20), and (22) are preferable.

R's in General Formula (I) each independently represent a substituent, and in the case where m is 2 or more, a plurality of R's may be different from each other.

Examples of the substituent represented by R include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group, an aryloxy group, a silyloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, an amino group (including an alkylamino group and an anilino group), an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, an alkylsulfonylamino or arylsulfonylamino group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, a sulfo group, an alkylsulfinyl or arylsulfinyl group, an alkylsulfonyl or arylsulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an arylazo or heterocyclic azo group, an imide group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, a phosphono group, and a silyl group. These will be described in detail below.

Examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a linear or branched alkyl group (a linear or branched substituted or unsubstituted alkyl group, and preferably an alkyl group having 1 to 30 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl, 2-chloroethyl, 2-cyanoethyl, and 2-ethylhexyl), a cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, for example, cyclohexyl and cyclopentyl, or a polycycloalkyl group, for example, a group having a polycyclic structure such as a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, for example, bicyclo[1,2,2]heptan-2-yl and bicyclo[2,2,2]octan-3-yl), and a tricycloalkyl group. Among these, a monocyclic cycloalkyl group and a bicycloalkyl group are preferable, and a monocyclic cycloalkyl group is particularly preferable),

a linear or branched alkenyl group (a linear or branched substituted or unsubstituted alkenyl group, which is preferably an alkenyl group having 2 to 30 carbon atoms, for example, vinyl, allyl, prenyl, geranyl, and oleyl), a cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, for example, 2-cyclopenten-1-yl and 2-cyclohexen-1-yl, a polycyclic alkenyl group, for example, a bicycloalkenyl group (preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, for example, bicyclo[2,2,1]hepto-2-en-1-yl and bicyclo[2,2,2]octo-2-en-4-yl), or a tricycloalkenyl group. Among these, a monocyclic cycloalkenyl group is particularly preferable), an alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, for example, an ethynyl group, a propargyl group, and a trimethylsilylethynyl group),

an aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, for example, phenyl, p-tolyl, naphthyl, m-chlorophenyl, and o-hexadecanoylaminophenyl), a heterocyclic group (preferably a substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, and monocyclic or ring-fused 5- to 7-membered heterocyclic group, more preferably a heterocyclic group of which ring-constituting atoms are selected from a carbon atom, a nitrogen atom, and a sulfur atom, and which has at least any one of hetero atoms including a nitrogen atom, an oxygen atom, and a sulfur atom, and still more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, for example, 2-furyl, 2-thienyl, 2-pyridyl, 4-pyridyl, 2-pyrimidinyl, and 2-benzothiazolyl), a cyano group, a hydroxyl group, a nitro group, a carboxyl group,

an alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, for example, methoxy, ethoxy, isopropoxy, tert-butoxy, n-octyloxy, and 2-methoxyethoxy), an aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, for example, phenoxy, 2-methylphenoxy, 2,4-di-tert-amylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy, and 2-tetradecanoylaminophenoxy), a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, for example, trimethylsilyloxy and tert-butyldimethylsilyloxy), a heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, with the heterocyclic moiety being preferably the heterocyclic moiety explained for the aforementioned heterocyclic group, and the heterocyclic oxy group being, for example, 1-phenyltetrazol-5-oxy or 2-tetrahydropyranyloxy),

an acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, and a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, for example, formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, and p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, for example, N,N-dimethylcarbamoyloxy, N,N-diethylcarbamoyloxy, morpholinocarbonyloxy, N,N-di-n-octylaminocarbonyloxy, and N-n-octylcarbamoyloxy), an alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, for example, methoxycarbonyloxy, ethoxycarbonyloxy, tert-butoxycarbonyloxy, and n-octylcarbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, for example, phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, and p-n-hexadecyloxyphenoxycarbonyloxy),

an amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, and a heterocyclic amino group having 0 to 30 carbon atoms, for example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, and N-1,3,5-triazin-2-ylamino), an acylamino group (preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, and a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, for example, formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, and 3,4,5-tri-n-octyloxyphenylcarbonylamino), an aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, for example, carbamoylamino, N,N-dimethylaminocarbonylamino, N,N-diethylaminocarbonylamino, and morpholinocarbonylamino), an alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, n-octadecyloxycarbonylamino, and N-methyl-methoxycarbonylamino),

an aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, for example, phenoxycarbonylamino, p-chlorophenoxycarbonylamino, and m-n-octyloxyphenoxycarbonylamino), a sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, for example, sulfamoylamino, N,N-dimethylaminosulfonylamino, and N-n-octylaminosulfonylamino), an alkylsulfonylamino or arylsulfonylamino group (preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, for example, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, and p-methylphenylsulfonylamino), a mercapto group,

an alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, for example, methylthio, ethylthio, and n-hexadecylthio), an arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, for example, phenylthio, p-chlorophenylthio, and m-methoxyphenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, in which a heterocyclic moiety is preferably the heterocyclic moiety explained for the aforementioned heterocyclic group, for example, 2-benzothiazolylthio and 1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfamoyl, N-(3-dodecyloxypropyl)sulfamoyl, N,N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, and N—(N′-phenylcarbamoyl)sulfamoyl), a sulfo group,

an alkylsulfinyl or arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms or a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, for example, methylsulfinyl, ethylsulfinyl, phenylsulfinyl, and p-methylphenylsulfinyl), an alkylsulfonyl or arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms or a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, for example, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, and p-methylphenylsulfonyl), an acyl group (preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, for example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, and p-n-octyloxyphenylcarbonyl), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, for example, phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, and p-tert-butylphenoxycarbonyl),

an alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, and n-octadecyloxycarbonyl), a carbamoyl group (preferably substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, for example, carbamoyl, N-methylcarbamoyl, N,N-dimethylcarbamoyl, N,N-di-n-octylcarbamoyl, and N-(methylsulfonyl)carbamoyl), an arylazo or heterocyclic azo group (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, or a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms (in which a heterocyclic moiety is preferably the heterocyclic moiety explained for the aforementioned heterocyclic group), for example, phenylazo, p-chlorophenylazo, and 5-ethylthio-1,3,4-thiadiazol-2-ylazo), an imide group (preferably a substituted or unsubstituted imide group having 2 to 30 carbon atoms, for example, N-succinimide and N-phthalimide), a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, for example, dimethylphosphino, diphenylphosphino, and methylphenoxyphosphino), a phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, for example, phosphinyl, dioctyloxyphosphinyl, and diethoxyphosphinyl),

a phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, for example, diphenoxyphosphinyloxy and dioctyloxyphosphinyloxy), a phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino and dimethylaminophosphinylamino), a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, for example, trimethylsilyl, tert-butyldimethylsilyl, and phenyldimethylsilyl), and a phosphono group (for example, PO₃H₂).

Among the above functional groups, in the functional groups having hydrogen atoms, the portion of hydrogen atoms in the functional groups may be substituted with any one of the above groups. Examples of the functional groups which can be introduced as substituents include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group, and specific examples thereof include a methylsulfonylaminocarbonyl group, a p-methylphenylsulfonylaminocarbonyl group, an acetylaminosulfonyl group, and a benzoylaminosulfonyl group.

Furthermore, R's are each preferably an acid group or a polymerizable group.

As the polymerizable group, known polymerizable groups which can be crosslinked by a radical, an acid, or heat can be used, and examples thereof include a group having an ethylenically unsaturated bond, a cyclic ether group (an epoxy group or an oxetane group), and a methylol group. In particular, a group having an ethylenically unsaturated bond is preferred, a (meth)acryloyl group is more preferable, and a (meth)acryloyl group derived from glycidyl (meth)acrylate and 3,4-epoxy-cyclohexylmethyl (meth)acrylate is particularly preferable.

In the present invention, the number of R's as polymerizable groups in the dye represented by General Formula (I) is preferably 1 or 2, and more preferably 1. By setting the number of polymerizable groups to such a range, decoloration can be more effectively inhibited. In particular, the effect is remarkably exhibited in the case of including a dye residue having a cationic site and an anionic site in a molecule.

As the acid group, a carboxyl group, a sulfo group, or a phosphoric acid group is preferable, and a carboxyl group is more preferable.

In the present invention, the number of R's as acid groups in the dye represented by General Formula (I) is preferably 1 to 3, and more preferably 1 or 2. By setting the number of acid groups to such a range, developability tends to be more improved. In particular, the effect is remarkably exhibited in the case where there is a dye residue having a cationic site and an anionic site in a molecule thereof.

m represents an integer of 0 to 6, preferably an integer of 1 to 4, and more preferably an integer of 1 to 3.

n represents an integer of 2 to 8, preferably an integer of 2 to 6, and more preferably an integer of 2 to 5.

m+n represents an integer of 2 to 8, preferably an integer of 2 to 7, and more preferably an integer of 3 to 6.

In General Formula (I), D's each represent a dye residue. The dye residue (hereinafter also referred to as a “dye structure”) is not particularly limited as long as it has a maximum absorption wavelength which is present in a range of 400 nm to 780 nm, and as the dye residue, a dye residue constituted with a cationic site and a counter anion, or a dye residue having a cationic site and an anionic site in a molecule thereof is preferable.

<<Dye-Derived Partial Structure>>

The dye residue D in the dye (A) is not particularly limited as long as it has a maximum absorption wavelength which is present in a range of 400 nm to 780 nm, and various dye residues having known dye structures can be applied. Examples of the known dye structure include dye structures derived from a dye selected from a dipyrromethene dye, a carbonium dye (a diphenylmethane dye, a triarylmethane dye, a xanthene dye, an acridine dye, and the like), a polymethine dye (an oxonol dye, a merocyanine dye, an arylidene dye, a styryl dye, a cyanine dye, a squarylium dye, a croconium dye, and the like), a subphthalocyanine dye, and metal complex dyes of these. Further, the dye residue used in the present invention may have a cationic site and an anionic site in the dye residue, or may be constituted with a cationic site and a counter anion. In the present invention, it is preferable that the dye residue is constituted with a cationic site and a counter anion. By constituting the dye residue with a cationic site and a counter anion, the transmittance at 450 nm can be further decreased, and the transmittance at 550 nm can further be increased.

Among these dye structures, from the viewpoint of color characteristics, dye structures derived from a dye selected from a dipyrromethene dye, a carbonium dye, and a polymethine dye are preferable, dye structures derived from a dye selected from a triarylmethane dye, a xanthene dye, a cyanine dye, a squarylium dye, a quinophthalone dye, a phthalocyanine dye, and a subphthalocyanine dye are more preferable, dye structures derived from a dye selected from a dipyrromethene dye, a triarylmethane dye, a xanthene dye, a cyanine dye, and a squarylium dye are still more preferable, and dye structures derived from a dye selected from xanthene dyes are most preferable.

Specific dye compounds which can form a dye structure are described in “New Edition of Dye Handbook” (edited by The Society of Synthetic Organic Chemistry, Japan; Maruzen Co., Ltd., 1970), “Color index” (The Society of Dyers and colourists), “Dye Handbook” (edited by Ogawara, et al.; Kodansha, Ltd., 1986), and the like.

For D in General Formula (I) in the dye (A), a particularly preferred dye (dye compound) which can form a dye-derived partial structure will be described in detail.

<<<Dipyrromethene Dye>>>

One of the embodiments of D in General Formula (I) in the dye (A) according to the present invention is a dye which has a partial structure derived from the dipyrromethene dye shown below as a partial structure of the dye site.

As the dipyrromethene dye in the present invention, a dipyrromethene compound, and a dipyrromethene metal complex compound obtained from a dipyrromethene compound with a metal or a metal compound are preferable.

Incidentally, in the present invention, a compound including a dipyrromethene structure is referred to as a dipyrromethene compound, and a complex in which the compound having a dipyrromethene structure is coordinated to a metal or a metal compound is referred to as a dipyrromethene metal complex compound.

As the dipyrromethene metal complex compound, a dipyrromethene metal complex compound obtained from a dipyrromethene compound represented by the following General Formula (M) with a metal or a metal compound and a tautomer thereof are preferable. Among these, a dipyrromethene metal complex compound represented by the following General Formula (7) and a dipyrromethene metal complex compound represented by the following General Formula (8) are exemplified as preferred embodiments, and the dipyrromethene metal complex compound represented by General Formula (8) is most preferable.

Dipyrromethene Metal Complex Compound Obtained from Dipyrromethene Compound Represented by General Formula (M) with Metal or a Metal Compound, and Tautomer Thereof

One of the preferred embodiments of D in General Formula (I) in the dye (A) is a dye structure which includes, as a dye site, a complex (hereinafter appropriately referred to as a “specific complex”) in which a compound (dipyrromethene compound) represented by the following General Formula (M) or a tautomer thereof is coordinated to a metal or a metal compound.

In General Formula (M), R⁴ to R¹⁰ each independently represent a hydrogen atom or a monovalent substituent, provided that there is no case where R⁴ and R⁹ are bonded to each other to form a ring.

When the compound represented by General Formula (M) is introduced into Q in General Formula (I), the introduction site is not particularly limited. However, in view of synthesis suitability, the compound is preferably introduced at any one site of R⁴ to R⁹, more preferably introduced at any one site of R⁴, R⁶, R⁷, and R⁹, and still more preferably introduced at any one site of R⁴ and R⁹.

In the case where R⁴ to R⁹ in General Formula (M) represent a monovalent substituent, examples of the monovalent substituent include the substituents exemplified in the section of the substituent group A which will be described later.

In the case where the monovalent substituents represented by R⁴ to R⁹ in General Formula (M) are each a group which can be further substituted, the group may further have the substituent(s) described for R⁴ to R⁹, and in the case where the group has two or more substituents, these substituents may be the same as or different from each other.

In General Formula (M), R⁴ and R⁵, R⁵ and R⁶, R⁷ and R⁸, and R⁸ and R⁹ may be each independently bonded to each other to form a 5-, 6-, or 7-membered saturated or unsaturated ring, provided that there is no case where R⁴ and R⁹ are bonded to each other to form a ring. In the case where the formed 5-, 6-, or 7-membered ring is a group which can be further substituted, the ring may be substituted with the substituents described for R⁴ to R⁹, and in the case where the ring is substituted with two or more substituents, these substituents may be the same as or different from each other.

In General Formula (M), in the case where R⁴ and R⁵, R⁵ and R⁶, R⁷ and R⁸, and R⁸ and R⁹ are each independently bonded to each other to form a 5-, 6-, or 7-membered saturated or unsaturated ring not having a substituent, examples of the 5-, 6-, or 7-membered saturated or unsaturated ring not having a substituent include a pyrrole ring, a furan ring, a thiophene ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, a pyrrolidine ring, a piperidine ring, a cyclopentene ring, a cyclohexene ring, a benzene ring, a pyridine ring, a pyrazine ring, and a pyridazine ring, and preferably a benzene ring or a pyridine ring.

R¹⁰ in General Formula (M) preferably represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. The halogen atom, the alkyl group, the aryl group, and the heterocyclic group have the same definitions as those of the halogen atom, the alkyl group, the aryl group, and the heterocyclic group, respectively, described in the section of the substituent group A which will be described later, and a preferred range thereof is also the same.

In the case where R¹⁰ represents an alkyl group, an aryl group, or a heterocyclic group, if the alkyl group, the aryl group, and the heterocyclic group are groups which can be further substituted, they may be substituted with the substituents described in the section of the substituent group A which will be described later. In the case where the groups are substituted with two or more substituents, the substituents may be the same as or different from each other.

Metal or Metal Compound

The specific complex in the present invention is the aforementioned complex in which the dipyrromethene compound represented by General Formula (M) or a tautomer thereof is coordinated to a metal or a metal compound.

Here, the metal or metal compound may be any types of metal or metal compound as long as they can form a complex, and examples thereof include a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, and a divalent metal chloride. Examples of the metal or metal compound include metals such as Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, and Fe, metal chlorides such as AlCl, InCl, FeCl, TiCl₂, SnCl₂, SiCl₂, and GeCl₂, metal oxides such as TiO and VO, and metal hydroxides such as Si(OH)₂.

Among these, in view of the stability, spectral characteristics, heat resistance, light fastness, and production suitability of the complex, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, or VO is preferable, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, or VO is more preferable, and Zn is particularly preferable.

Next, a more preferred range of the specific complex of the compound represented by General Formula (M) in the present invention will be described.

A preferred range of the specific complex in the present invention is a range in which in General Formula (M), R⁴ and R⁹ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a silyl group, a hydroxyl group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an amino group, an anilino group, a heterocyclic amino group, a carbonamide group, a ureido group, an imide group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamide group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a phosphinoylamino group; R⁵ and R⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxyl group, a cyano group, a nitro group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an imide group, an alkoxycarbonylamino group, a sulfonamide group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group; R⁶ and R⁷ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a silyl group, a hydroxyl group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an anilino group, a carbonamide group, a ureido group, an imide group, an alkoxycarbonylamino group, a sulfonamide group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, or a phosphinoylamino group; R¹⁰ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group; and the metal or metal compound is Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, or V═O.

A more preferred range of the specific complex in the present invention is a range in which in General Formula (M), R⁴ and R⁹ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an amino group, a heterocyclic amino group, a carbonamide group, a ureido group, an imide group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamide group, an azo group, an alkylsulfonyl group, an arylsulfonyl group, or a phosphinoylamino group; R⁵ and R⁸ are each independently an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an imide group, an alkylsulfonyl group, an aryl sulfonyl group, or a sulfamoyl group; R⁶ and R⁷ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, a carbonamide group, a ureido group, an imide group, an alkoxycarbonylamino group, a sulfonamide group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group; R¹⁰ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group; and the metal or metal compound is Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, or V═O.

A particularly preferred range of the specific complex in the present invention is a range in which in General Formula (M), R⁴ and R⁹ are each a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an amino group, a heterocyclic amino group, a carbonamide group, a ureido group, an imide group, an alkoxycarbonylamino group, a sulfonamide group, an azo group, an alkylsulfonyl group, an arylsulfonyl group, or a phosphinoylamino group; R⁵ and R⁸ are each independently an alkyl group, an aryl group, a heterocyclic group, a cyano group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, or an arylsulfonyl group; R⁶ and R⁷ are each independently a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group; R¹⁰ is a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group; and the metal or metal compound is Zn, Cu, Co, or V═O.

Moreover, a dipyrromethene metal complex compound represented by General Formula (7) or (8), which will be described in detail below, is also a particularly preferred embodiment of the dipyrromethene dye.

Dipyrromethene Metal Complex Compound Represented by General Formula (7)

One of the suitable embodiments of D in General Formula (I) in the dye (A) is a dye structure derived from a dipyrromethene metal complex compound represented by the following General Formula (7).

In General Formula (7), R⁴ to R⁹ each independently represent a hydrogen atom or a monovalent substituent, and R¹⁰ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal atom or a metal compound. X¹ represents a group which can be bonded to Ma, X² represents a group which neutralizes the charge of Ma, and X¹ and X² may be bonded to each other to form a 5-, 6-, or 7-membered ring together with Ma, provided that there is no case where R⁴ and R⁹ are bonded to each other to form a ring.

Incidentally, the dipyrromethene metal complex compound represented by General Formula (7) includes a tautomer.

In the case where the dipyrromethene metal complex compound represented by General Formula (7) is introduced into Q in General Formula (I), the introduction site is not particularly limited. However, in view of synthesis suitability, the compound is preferably introduced at any one site of R⁴ to R⁹, more preferably introduced at any one site of R⁴, R⁶, R⁷, and R⁹, and still more preferably introduced at any one site of R⁴ and R⁹.

In the case where the dye (A) has an alkali-soluble group, as a method for introducing the alkali-soluble group, a method for introducing the alkali-soluble group to one, two, or more substituents out of R⁴ to R¹⁰, X¹ and X² in General Formula (7) can be used. Among these substituents, any one of R⁴ to R⁹ and X¹ is preferable, any one of R⁴, R⁶, R⁷, and R⁹ is more preferable, and any one of R⁴ and R⁹ is still more preferable.

The dipyrromethene metal complex compound represented by General Formula (7) may have a functional group other than the alkali-soluble group as long as the effects of the present invention are not diminished.

R⁴ to R⁹ in General Formula (7) have the same definitions as R⁴ to R⁹ in General Formula (M), and preferred embodiments thereof are also the same.

In General Formula (7), Ma represents a metal atom or a metal compound. The metal atom or metal compound may be any type as long as it is a metal atom or a metal compound which can form a complex, and examples thereof include a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or a divalent metal chloride.

Examples of the metal atom or metal compound include Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, and Fe; metal chlorides such as AlCl, InCl, FeCl, TiCl₂, SnCl₂, SiCl₂, and GeCl₂; metal oxides such as TiO and V═O; and metal hydroxides such as Si(OH)₂.

Among these, in view of stability, spectral characteristics, heat resistance, light fastness, and production suitability of the complex, as the metal atom or metal compound, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, and V═O are preferable, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, and V═O are more preferable, Zn, Co, V═O, and Cu are particularly preferable, and Zn is most preferable.

In General Formula (7), R¹⁰ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and is preferably a hydrogen atom.

In General Formula (7), X¹ may be any group as long as the group can be bonded to Ma, and specific examples thereof include water, alcohols (for example, methanol, ethanol, and propanol), and compounds disclosed in “Metal Chelates” ([1] Takeichi Sakaguchi and Kagehira Ueno (1995, Nankodo Co., Ltd.), [2] (1996), [3] (1997), and the like). Among these, in view of production thereof, water, a carboxylic acid compound, and alcohols are preferable, and water and a carboxylic acid compound are more preferable.

In General Formula (7), examples of the “group which neutralizes the charge of Ma” represented by X² include a halogen atom, a hydroxyl group, a carboxylic acid group, a phosphoric acid group, a sulfonic acid group, and the like. Among these, in view of production thereof, a halogen atom, a hydroxyl group, a carboxylic acid group, and a sulfonic acid group are preferable, and a hydroxyl group and a carboxylic acid group are more preferable.

In General Formula (7), X¹ and X² may be bonded to each other to form a 5-, 6-, or 7-membered ring together with Ma. The formed 5-, 6-, or 7-membered ring may be a saturated or unsaturated ring. In addition, the 5-, 6-, or 7-membered ring may be constituted only with carbon atoms or may form a heterocycle having at least one atom selected from a nitrogen atom, an oxygen atom, or/and a sulfur atom.

In a preferred embodiment of the compound represented by General Formula (7), R⁴ to R⁹ each independently represent the group described as the preferred embodiment of R⁴ to R⁹; R¹⁰ represents the group described as the preferred embodiment of R¹⁰, Ma is Zn, Cu, Co, or V═O; X¹ is water or a carboxylic acid compound; X² is a hydroxyl group or a carboxylic acid group; and X¹ and X² may be bonded to each other to form a 5- or 6-membered ring.

One of suitable embodiments of D in General Formula (I) in the dye (A) is a dye structure derived from a dipyrromethene metal complex compound represented by the following General Formula (8).

In General Formula (8), R¹¹ and R¹⁶ each independently represent an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group. R¹² to R¹⁵ each independently represent a hydrogen atom or a substituent. R¹⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal atom or a metal compound. X² and X³ each independently represent NR (in which R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), a nitrogen atom, an oxygen atom, or a sulfur atom. Y¹ and Y² each independently represent NR^(c) (in which R^(c) represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), a nitrogen atom or a carbon atom. R¹¹ and Y¹ may be bonded to each other to form a 5-, 6-, or 7-membered ring, and R¹⁶ and Y² may be bonded to each other to form a 5-, 6-, or 7-membered ring. X¹ represents a group which can be bonded to Ma, and a represents 0, 1, or 2.

Incidentally, the dipyrromethene metal complex compound represented by General Formula (8) includes a tautomer.

The site at which the dipyrromethene metal complex compound represented by General Formula (8) is introduced into Q in General Formula (I) is not particularly limited as long as the effects of the present invention are not diminished. However, the site is preferably at least one of R¹¹ to R¹⁷, X¹, Y¹ to Y². Among these, in view of synthesis suitability, it is preferable that the compound is introduced at one of R¹¹ to R¹⁶ and X¹. In a more preferred embodiment, the compound is introduced at one of R¹¹, R¹³, R¹⁴, and R¹⁶. In a still more preferred embodiment, the compound is introduced at one of R¹¹ and R¹⁶.

In the case where the dye (A) has an alkali-soluble group, if a dye monomer or a structural unit having the alkali-soluble group is used as a method for introducing the alkali-soluble group, it is possible to use a method for introducing the alkali-soluble group into one, two, or more substituents out of R¹¹ to R¹⁷, X¹, Y¹ to Y² in General Formula (8). Among these substituents, one of R¹¹ to R¹⁶ and X¹ is preferable, one of R¹¹, R¹³, R¹⁴, and R¹⁶ is more preferable, and one of R¹¹ and R¹⁶ is still more preferable.

The dipyrromethene metal complex compound represented by General Formula (8) may have a functional group other than the alkali-soluble group as long as the effects of the present invention are not diminished.

In General Formula (8), R¹² to R¹⁵ have the same definitions as R⁵ to R⁸ in General Formula (M), and preferred embodiments thereof are also the same. R¹⁷ has the same definition as R¹⁰ in General Formula (M), and preferred embodiments thereof are also the same. Ma has the same definition as Ma in General Formula (7), and preferred ranges thereof are also the same.

More specifically, among R¹² to R¹⁵ in General Formula (8), as R¹² and R¹⁵, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a nitrile group, an imide group, and a carbamoylsulfonyl group are preferable, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, a nitrile group, an imide group, and a carbamoylsulfonyl group are more preferable, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a nitrile group, an imide group, and a carbamoylsulfonyl group are still more preferable, and an alkoxycarbonyl group, an aryloxycarbonyl group, and a carbamoyl group are particularly preferable.

As R¹³ and R¹⁴, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group are preferable, and a substituted or unsubstituted alkyl group and a substituted or unsubstituted aryl group are more preferable. Specific examples of the more preferable alkyl group, an aryl group, and heterocyclic group include the same specific examples as listed for R⁶ and R⁷ of General Formula (M).

In General Formula (8), R¹¹ and R¹⁶ each represent an alkyl group (a linear, branched, or cyclic alkyl group preferably having 1 to 36 carbon atoms, and more preferably having 1 to 12 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a hexyl group, a 2-ethylhexyl group, a dodecyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a 1-adamantyl group), an alkenyl group (an alkenyl group preferably having 2 to 24 carbon atoms, and more preferably having 2 to 12 carbon atoms, for example, a vinyl group, an allyl group, and a 3-buten-1-yl group), an aryl group (an aryl group preferably having 6 to 36 carbon atoms, and more preferably having 6 to 18 carbon atoms, for example, a phenyl group and a naphthyl group), a heterocyclic group (a heterocyclic group preferably having 1 to 24 carbon atoms, and more preferably having 1 to 12 carbon atoms, for example, a 2-thienyl group, a 4-pyridyl group, a 2-furyl group, a 2-pyrimidinyl group, a 2-pyridyl group, a 2-benzothiazolyl group, a 1-imidazolyl group, a 1-pyrazolyl group, and a benzotriazol-1-yl group), an alkoxy group (an alkoxy group preferably having 1 to 36 carbon atoms, and more preferably having 1 to 18 carbon atoms, for example, a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, a hexyloxy group, a 2-ethylhexyloxy group, a dodecyloxy group, and a cyclohexyloxy group), an aryloxy group (an aryloxy group preferably having 6 to 24 carbon atoms, and more preferably having 1 to 18 carbon atoms, for example, a phenoxy group and a naphthyloxy group), an alkylamino group (an alkylamino group preferably having 1 to 36 carbon atoms, and more preferably having 1 to 18 carbon atoms, for example, a methylamino group, an ethylamino group, a propylamino group, a butylamino group, a hexylamino group, a 2-ethylhexylamino group, an isopropylamino group, a tert-butylamino group, a tert-octylamino group, a cyclohexylamino group, an N,N-diethylamino group, an N,N-dipropylamino group, an N,N-dibutylamino group, and an N-methyl-N-ethylamino group), an arylamino group (an arylamino group preferably having 6 to 36 carbon atoms, and more preferably having 6 to 18 carbon atoms, for example, a phenylamino group, a naphthylamino group, an N,N-diphenylamino group, and an N-ethyl-N-phenylamino group), or a heterocyclic amino group (a heterocyclic amino group preferably having 1 to 24 carbon atoms, and more preferably having 1 to 12 carbon atoms, for example, a 2-aminopyrrole group, a 3-aminopyrazole group, a 2-aminopyridine group, and a 3-aminopyridine group).

Among the above groups, as R¹¹ and R¹⁶, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkylamino group, an arylamino group, and a heterocyclic amino group are preferable, an alkyl group, an alkenyl group, an aryl group, and a heterocyclic group are more preferable, an alkyl group, an alkenyl group, and an aryl group are still more preferable, and an alkyl group is particularly preferable.

In General Formula (8), in the case where the alkyl group, the alkenyl group, the aryl group, the heterocyclic group, the alkoxy group, the aryloxy group, the alkylamino group, the arylamino group, or the heterocyclic amino group represented by R¹¹ and R¹⁶ is a group which can be further substituted, the group may be substituted with the substituents described in the section of the substituent group A which will be described later. In the case where the group is substituted with two or more substituents, these substituents may be the same as or different from each other.

In General Formula (8), X² and X³ each independently represent NR, a nitrogen atom, an oxygen atom, or a sulfur atom. Here, R represents a hydrogen atom, an alkyl group (a linear, branched, or cyclic alkyl group preferably having 1 to 36 carbon atoms, and more preferably having 1 to 12 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a hexyl group, a 2-ethylhexyl group, a dodecyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a 1-adamantyl group), an alkenyl group (an alkenyl group preferably having 2 to 24 carbon atoms, and more preferably having 2 to 12 carbon atoms, for example, a vinyl group, an allyl group, and a 3-buten-1-yl group), an aryl group (an aryl group preferably having 6 to 36 carbon atoms, and more preferably having 6 to 18 carbon atoms, for example, a phenyl group and a naphthyl group), a heterocyclic group (a heterocyclic group preferably having 1 to 24 carbon atoms, and more preferably having 1 to 12 carbon atoms, for example, a 2-thienyl group, a 4-pyridyl group, a 2-furyl group, a 2-pyrimidinyl group, a 1-pyridyl group, a 2-benzothiazolyl group, a 1-imidazolyl group, a 1-pyrazolyl group, and a benzotriazol-1-yl group), an acyl group (an acyl group preferably having 1 to 24 carbon atoms, and more preferably having 2 to 18 carbon atoms, for example, an acetyl group, a pivaloyl group, a 2-ethylhexyl group, a benzoyl group, and a cyclohexanoyl group), an alkylsulfonyl group (an alkylsulfonyl group preferably having 1 to 24 carbon atoms, and more preferably having 1 to 18 carbon atoms, for example, a methylsulfonyl group, an ethylsulfonyl group, an isopropylsulfonyl group, and a cyclohexylsulfonyl group), and an arylsulfonyl group (an arylsulfonyl group preferably having 6 to 24 carbon atoms, and more preferably having 6 to 18 carbon atoms, for example, a phenylsulfonyl group and a naphthylsulfonyl group).

In General Formula (8), Y¹ and Y² each independently represent NR^(c), a nitrogen atom, or a carbon atom. R^(c) has the same definition as R of X² and X³, and the preferred embodiments thereof are also the same.

In General Formula (8), R¹¹ and Y¹ may be bonded to each other to form a 5-membered ring (for example, a cyclopentane ring, a pyrrolidine ring, a tetrahydrofuran ring, a dioxolane ring, a tetrahydrothiophene ring, a pyrrole ring, a furan ring, a thiophene ring, an indole ring, a benzofuran ring, and a benzothiophene ring), a 6-membered ring (for example, a cyclohexane ring, a morpholine ring, a tetrahydropyran ring, a dioxane ring, a pentamethylene sulfide ring, a dithiane ring, a benzene ring, a piperidine ring, a piperazine ring, a pyridazine ring, a quinoline ring, and a quinazoline ring), or a 7-membered ring (for example, a cycloheptane ring and a hexamethylene imine ring) together with a carbon atom.

In General Formula (8), R¹⁶ and Y² may be bonded to each other to form a 5-membered ring (for example, a cyclopentane ring, a pyrrolidine ring, a tetrahydrofuran ring, a dioxolane ring, a tetrahydrothiophene ring, a pyrrole ring, a furan ring, a thiophene ring, an indole ring, a benzofuran ring, and a benzothiophene ring), a 6-membered ring (for example, a cyclohexane ring, a piperidine ring, a piperazine ring, a morpholine ring, a tetrahydropyran ring, a dioxane ring, a pentamethylene sulfide ring, a dithiane ring, a benzene ring, a pyridazine ring, a quinoline ring, and a quinazoline ring), or a 7-membered ring (for example, a cycloheptane ring and a hexamethyleneimine ring) together with a carbon atom.

In General Formula (8), in the case where the 5-, 6-, and 7-membered rings formed by mutual bonding of R¹¹ and Y¹ as well as R¹⁶ and Y² are substitutable rings, the rings may be substituted with the substituents described in the section of the substituent group A which will be described later. In the case where the rings are substituted with two or more substituents, these substituents may be the same as or different from each other.

In General Formula (8), it is preferable that R¹¹ and R¹⁶ are each independently a monovalent substituent of which an −Es' value as a steric parameter is 1.5 or more. The −Es' value is more preferably 2.0 or more, still more preferably 3.5 or more, and particularly preferably 5.0 or more.

Here, the −Es' value as a steric parameter is a parameter which represents steric bulkiness of a substituent. As the value, the −Es' value disclosed in the document (J. A. Macphee, et al, Tetrahedron, Vol. 34, pp 3553-3562, and Chemistry Special Edition 107, Structure-activity Correlation and Drug Design, edited by Toshio Fujita, published on Feb. 20, 1986 (Kagaku-Dojin Publishing Company, Inc)) is used.

In General Formula (8), X¹ represents a group which can be bonded to Ma. Specific examples thereof include the same group as represented by X¹ in General Formula (7), and the preferred embodiments are also the same. a represents 0, 1, or 2.

With respect to a preferred embodiment of the compound represented by General Formula (8), R¹² to R¹⁵ are each independently one in the preferred embodiment cited in the description of R⁵ to R⁸ in General Formula (M), R¹⁷ is one in the preferred embodiment cited in the description of R¹⁰ in General Formula (M), Ma is Zn, Cu, Co, or V═O, X² is NR (in which R represents a hydrogen atom or an alkyl group), a nitrogen atom, or an oxygen atom, X³ is NR (in which R represents a hydrogen atom or an alkyl group) or an oxygen atom, Y¹ is NR^(c) (in which R^(c) represents a hydrogen atom or an alkyl group), a nitrogen atom, or a carbon atom, Y² is a nitrogen atom or a carbon atom, R¹¹ and R¹⁶ are each independently an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an alkylamino group, X¹ is a group bonded via an oxygen atom, and a is 0 or 1. R¹¹ and Y¹ may be bonded to each other to form a 5- or 6-membered ring, or R¹⁶ and Y² may be bonded to each other to form a 5- or 6-membered ring.

With respect to a more preferred embodiment of the compound represented by General Formula (8), R¹² to R¹⁵ are each independently one in the preferred embodiment cited in the description of R⁵ to R⁸ in the compound represented by General Formula (M), R¹⁷ is one in the preferred embodiment cited in the description of R¹⁰ in General Formula (M), Ma is Zn, X² and X³ are each an oxygen atom, Y¹ is NH, Y² is a nitrogen atom, R¹¹ and R¹⁶ are each independently an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an alkylamino group, X¹ is a group bonded via an oxygen atom, and a is 0 or 1. R¹¹ and Y¹ may be bonded to each other to form a 5- or 6-membered ring, or R¹⁶ and Y² may be bonded to each other to form a 5- or 6-membered ring.

From the viewpoint of coloring ability, the molar absorption coefficient of the dipyrromethene metal complex compound represented by General Formulae (7) and (8) is preferably as high as possible. Further, from the viewpoint of improving color purity, the maximum absorption wavelength λmax is preferably 520 nm to 580 nm, and more preferably 530 nm to 570 nm. If the value is within this range, it is possible to manufacture a color filter having excellent color reproducibility by using the coloring composition of the present invention.

Furthermore, an absorbance at the maximum absorption wavelength (λmax) of the dye (A) having a dye structure derived from a dipyrromethene dye is preferably 1,000 times or more, more preferably 10,000 times or more, and still more preferably 100,000 times or more the absorbance at 450 nm. If the ratio is within this range, particularly in the case where a blue color filter is manufactured using the coloring composition of the present invention, a color filter having a higher transmittance can be formed. Incidentally, the maximum absorption wavelength and the molar absorption coefficient are measured by a spectrophotometer Cary 5 (manufactured by Varian, Inc.).

From the viewpoint of solubility, it is preferable that the melting points of the dipyrromethene metal complex compounds represented by General Formulae (7) and (8) are not too high.

The dipyrromethene metal complex compounds represented by General Formulae (7) and (8) can be synthesized by the methods described in U.S. Pat. No. 4,774,339A, 5,433,896A, JP2001-240761A, JP2002-155052A, JP3614586B, Aust. J. Chem., 1965, 11, 1835-1845, J. H. Boger, et al., Heteroatom Chemistry, Vol. 1, No. 5,389 (1990), and the like. Specifically, the method described in paragraphs “0131” to “0157” of JP2008-292970A can be applied.

Specific examples of the dipyrromethene dye are shown below, but the present invention is not limited thereto. Further, the dipyrromethene compound which forms a structure employed in Examples, which will be described later, is also preferably used. Hereinbelow, X is selected from those obtained by removing charges from a counter anion X group which will be described later.

Among the specific examples, (PM-8) and (PM-10) are particularly preferable from the viewpoints of color characteristics and heat resistance.

<<<Triarylmethane Dye>>>

One of the embodiments of D in General Formula (I) in the dye according to the present invention is one having a partial structure derived from a triarylmethane dye (triarylmethane compound). Examples of the dye (A) include a dye which has, as a partial structure of a dye site, a partial structure derived from a compound (triarylmethane compound) represented by the following General Formula (TP). The triarylmethane compounds in the present invention collectively refer to compounds having a dye site containing a triarylmethane skeleton in a molecule thereof.

In General Formula (TP), Rtp¹ to Rtp⁴ each independently represent a hydrogen atom, an alkyl group, or an aryl group. Rtp⁵ represents a hydrogen atom, an alkyl group, an aryl group, or NRtp⁹Rtp¹⁰ (in which Rtp⁹ and Rtp¹⁰ represent a hydrogen atom, an alkyl group, or an aryl group). Rtp⁶, Rtp⁷, and Rtp⁸ represent substituents. a, b, and c represent an integer of 0 to 4. In the case where a, b, and c are 2 or more, Rtp⁶, Rtp⁷, and Rtp⁸ may be linked to each other to form a ring. X⁻ represents an anion. In the case where X⁻ is not present, at least one of Rtp¹ to Rtp⁷ contains an anion.

Rtp¹ to Rtp⁶ are preferably a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, or a phenyl group. Rtp⁵ is preferably a hydrogen atom or NRtp⁹Rtp¹⁰, and particularly preferably NRtp⁹Rtp¹⁰. Rtp⁹ and Rtp¹⁰ are preferably a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, or a phenyl group. As the substituents represented by Rtp⁶, Rtp⁷, and Rtp⁸, the substituents exemplified in the section of the substituent group A which will be described later can be used. In particular, a linear or branched alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, an aryl group having 6 to 15 carbon atoms, a carboxyl group, or a sulfo group is preferable, and a linear or branched alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, a phenyl group, or a carboxyl group is more preferable. In particular, Rtp⁶ and Rtp⁸ are preferably an alkyl group having 1 to 5 carbon atoms, and Rtp⁷ is preferably an alkenyl group (particularly preferably a phenyl group formed by linking two adjacent alkenyl groups to each other), a phenyl group, or a carboxyl group.

a, b, or c each independently represents an integer of 0 to 4. In particular, a and b are preferably 0 to 1, and c is preferably 0 to 2.

X⁻ is preferably selected from the counter anion X group which will be described later.

Specific examples of the compounds represented by General Formula (TP) are shown below, but the present invention is not limited thereto. X⁻ is preferably selected from the counter anion X group which will be described later.

Among the specific examples, (tp-4), (tp-5), (tp-6), and (tp-8) are particularly preferable from the viewpoints of color characteristics and heat resistance.

<<<Xanthene Dye>>>

A preferred embodiment of D in General Formula (I) in the dye in the present invention is one having a partial structure derived from a xanthene dye (xanthene compound). Examples of the dye (A) include a dye which has, as a partial structure of a dye site, a partial structure derived from a xanthene compound represented by the following General Formula (J).

In General Formula (J), R⁸¹, R⁸², R⁸³, and R⁸⁴ each independently represent a hydrogen atom or a monovalent substituent. R⁸⁵'s each independently represent a monovalent substituent, and m represents an integer of 0 to 5. X⁻ represents a counter anion. In the case where X⁻ is not present, at least one of R⁸¹ to R⁸⁵ contains an anion.

The substituents which may be contained in R⁸¹ to R⁸⁴ and R⁸⁵ in General Formula (J) have the same definitions as the substituents exemplified in the section of the substituent group A which will be described later.

In General Formula (J), R⁸¹ and R⁸², R⁸³ and R⁸⁴, and R⁸⁵'s in a case where m is 2 or more may be each independently bonded to each other to form a 5-, 6-, or 7-membered saturated ring or a 5-, 6-, or 7-membered unsaturated ring. In the case where the formed 5-, 6-, or 7-membered ring is a group which can be further substituted, the ring may be substituted with the substituents described for R⁸¹ to R⁸⁵. In the case where the ring is substituted with two or more substituents, these substituents may be the same as or different from each other.

In General Formula (J), in the case where R⁸¹ and R⁸², R⁸³ and R⁸⁴, and R⁸⁵'s in a case where m is 2 or more are each independently bonded to each other to form 5-, 6-, and 7-membered saturated rings not having a substituent or form 5-, 6-, and 7-membered unsaturated rings, examples of the 5-, 6-, and 7-membered saturated rings not having a substituent or the 5-, 6-, and 7-membered unsaturated rings include a pyrrole ring, a furan ring, a thiophene ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, a pyrrolidine ring, a piperidine ring, a cyclopentene ring, a cyclohexene ring, a benzene ring, a pyridine ring, a pyrazine ring, and a pyridazine ring, and preferably a benzene ring and a pyridine ring.

R⁸² and R⁸³ are particularly preferably a hydrogen atom or a substituted or unsubstituted alkyl group, and R⁸¹ and R⁸⁴ are particularly preferably a substituted or unsubstituted alkyl group or phenyl group. Further, R⁸⁵ is preferably a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a sulfo group, a sulfonamide group, a carboxyl group, or an amide group, and more preferably a sulfo group, a sulfonamide group, a carboxyl group, or an amide group. R⁸⁵ is preferably bonded to a portion adjacent to carbon linked to a xanthene ring. The substituent contained in the phenyl group represented by R⁸¹ and R⁸⁴ is most preferably a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a sulfo group, a sulfonamide group, or a carboxyl group.

It is preferable that X⁻ is selected from the counter anion X group which will be described later.

The compounds having xanthene skeletons represented by General Formula (J) may be synthesized using methods disclosed in literature. Specifically, the methods disclosed in Tetrahedron Letters, 2003, vol. 44, No. 23, pp. 4355 to 4360; Tetrahedron, 2005, vol. 61, No. 12, pp. 3097 to 3106; and the like can be applied.

Specific examples of the xanthene compounds are shown below, but the present invention is not limited thereto. Further, the compound which forms a xanthene structure used in Examples, which will be described later, is also preferably used. It is preferable that X⁻ is selected from the counter anion X group which will be described later.

TABLE 1

No. R¹ R² R³ R⁴ (XT-1) Me Me Me Me (XT-2) Et Et Et Et (XT-3) n-Pr n-Pr n-Pr n-Pr (XT-4) i-Pr i-Pr i-Pr i-Pr (XT-5) n-Bu n-Bu n-Bu n-Bu (XT-6) sec-Bu sec-Bu sec-Bu sec-Bu (XT-7) i-Bu i-Bu i-Bu i-Bu (XT-8) tert-Bu tert-Bu tert-Bu tert-Bu (XT-9) n-C6H13 n-C6H13 n-C6H13 n-C6H13 (XT-10) n-C18H37 n-C18H37 n-C18H37 n-C18H37 (XT-11) Me Et Me Et (XT-12) —CH2CH2OCH2CH2— —CH2CH2OCH2CH2— (XT-13) —(CH2)5— —(CH2)5— (XT-14) —(CH2)4— —(CH2)4— (XT-15) —(CH2)5— —(CH2)4— (XT-16) CH2Ph CH2Ph CH2Ph CH2Ph (XT-17) Et CH2CH2OMe Et CH2CH2OMe (XT-18) Me cyclo-C6H11 Me cyclo-C6H11 (XT-19) CH2C≡CH CH2C≡CH CH2C≡CH CH2C≡CH (XT-20) CH2CH═CH2 CH2CH═CH2 CH2CH═CH2 CH2CH═CH2 (XT-21) Me H Me H (XT-22) Et H Et H (XT-23) n-Pr H n-Pr H (XT-24) i-Pr H i-Pr H (XT-25) n-Bu H n-Bu H (XT-26) H H H H (XT-27) i-Bu H i-Bu H (XT-28) tert-Bu H tert-Bu H (XT-29) n-C6H13 H n-C6H13 H (XT-30) n-C18H37 H n-C18H37 H (XT-31) Ph H Ph H (XT-32) CH2Ph H CH2Ph H (XT-33) cyclo-C6H11 H cyclo-C6H11 H (XT-34) cyclo-C5H9 H cyclo-C5H9 H (XT-35) CH2C≡CH H CH2C≡CH H (XT-36) CH2CH═CH2 H CH2CH═CH2 H (XT-37)

H

H (XT-38)

H

H

TABLE 2

No. R¹ R² R³ R⁴ (XT-39) Me Me Me Me (XT-40) Et Et Et Et (XT-41) n-Pr n-Pr n-Pr n-Pr (XT-42) i-Pr i-Pr i-Pr i-Pr (XT-43) n-Bu n-Bu n-Bu n-Bu (XT-44) sec-Bu sec-Bu sec-Bu sec-Bu (XT-45) i-Bu i-Bu i-Bu i-Bu (XT-46) tert-Bu tert-Bu tert-Bu tert-Bu (XT-47) n-C6H13 n-C6H13 n-C6H13 n-C6H13 (XT-48) n-C18H37 n-C18H37 n-C18H37 n-C18H37 (XT-49) Me Et Me Et (XT-50) —CH2CH2OCH2CH2— —CH2CH2OCH2CH2— (XT-51) —(CH2)5— —(CH2)5— (XT-52) —(CH2)4— —(CH2)4— (XT-53) —(CH2)5— —(CH2)4— (XT-54) CH2Ph CH2Ph CH2Ph CH2Ph (XT-55) Et CH2CH2OMe Et CH2CH2OMe (XT-56) Me cyclo-C6H11 Me cyclo-C6H11 (XT-57) CH2C≡CH CH2C≡CH CH2C≡CH CH2C≡CH (XT-58) CH2CH═CH2 CH2CH═CH2 CH2CH═CH2 CH2CH═CH2 (XT-59) Me H Me H (XT-60) Et H Et H (XT-61) n-Pr H n-Pr H (XT-62) i-Pr H i-Pr H (XT-63) H H H H (XT-64) sec-Bu H sec-Bu H (XT-65) i-Bu H i-Bu H (XT-66) tert-Bu H tert-Bu H (XT-67) n-C6H13 H n-C6H13 H (XT-68) n-C18H37 H n-C18H37 H (XT-69) Ph H Ph H (XT-70) CH2Ph H CH2Ph H (XT-71) cyclo-C6H11 H cyclo-C6H11 H (XT-72) cyclo-C5H9 H cyclo-C5H9 H (XT-73) CH2C≡CH H CH2C≡CH H (XT-74) CH2CH═CH2 H CH2CH═CH2 H (XT-75)

H

H (XT-76)

H

H

<<<Cyanine Dye>>>

One of the embodiments of D in General Formula (I) in the dye according to the present invention is a dye which has a partial structure derived from a cyanine dye (cyanine compound). Examples of the dye (A) include a dye which has, as a partial structure of a dye site, a partial structure derived from a compound (cyanine compound) represented by the following General Formula (PM). The cyanine compounds in the present invention collectively refer to compounds having a dye site containing a cyanine skeleton in a molecule thereof.

In General Formula (PM), a ring Z¹ and a ring Z² each independently represent a heterocycle which may have a substituent. 1 represents an integer of 0 to 3, and X⁻ represents an anion.

Examples of the ring Z¹ and the ring Z² each independently include oxazole, benzoxazole, oxazoline, thiazole, thiazoline, benzothiazole, indolenine, benzoindolenine, and 1,3-thiadiazine.

The substituents which may be contained in the ring Z¹ and the ring Z² are the same substituents exemplified in the section of the substituent group A which will be described later. X⁻ represents a counter anion. X⁻ is preferably selected from the counter anion X group which will be described later.

The compound represented by General Formula (PM) is preferably a compound represented by the following General Formula (PM-2).

In General Formula (PM-2), the ring Z⁵ and the ring Z⁶ each independently represent a benzene ring which may have a substituent or a naphthalene ring which may have a substituent. X⁻ represents a counter anion.

n represents an integer of 0 to 3.

A¹ and A² each independently represent an oxygen atom, a sulfur atom, a selenium atom, a carbon atom, or a nitrogen atom.

R¹ and R² each independently represent a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.

R³ and R⁴ each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, or a divalent aliphatic hydrocarbon group having 2 to 6 carbon atoms, which is formed when one R³ and one R⁴ are combined with each other.

a and b each independently represent an integer of 0 to 2.

Specific examples of the cyanine compound are shown below, but the present invention is not limited thereto. X⁻ is preferably selected from the counter anion X group which will be described later.

Among the specific examples, the structures represented by (pm-1) to (pm-6), (pm-9), and (pm-10) are preferable, and among these, the dye structures represented by (pm-1), (pm-2), and (pm-10) are particularly preferable, from the viewpoints of color characteristics and heat resistance.

<<<Subphthalocyanine Compound>>>

One of the embodiments of D in General Formula (I) in the dye according to the present invention is one having a partial structure derived from a subphthalocyanine dye (phthalocyanine compound). Examples of the dye (A) include a dye which has, as a partial structure of a dye site, a partial structure derived from a compound (subphthalocyanine compound) represented by the following General Formula (SP). The subphthalocyanine compounds in the present invention collectively refer to compounds having a dye site including a subphthalocyanine skeleton in a molecule thereof. In the present invention, the following compound forms a cationic site, but, for example, a boron atom in General Formula (SP) can form a cationic site.

In General Formula (SP), Z¹ to Z¹² each independently represent a hydrogen atom, an alkyl group, an aryl group, a hydroxyl group, a mercapto group, an amino group, an alkoxy group, an aryloxy group, or a thioether group. X represents a counter anion. In the case where X⁻ is not present, at least one of Z¹ to Z¹² contains an anion.

General Formula (SP) will be described in detail.

The alkyl group which may be contained in Z¹ to Z¹² in General Formula (SP) represents a linear or branched substituted or unsubstituted alkyl group. In particular, Z¹ to Z¹² preferably have 1 to 20 carbon atoms, and more preferably have 1 to 10 carbon atoms. Examples of the substituents which may be contained in Z¹ to Z¹² include the substituents exemplified in the section of the substituent group A which will be described later, and among those, a fluorine atom, a hydroxyl group, and a mercapto group are particularly preferable.

X⁻ is preferably selected from the counter anion X group which will be described later.

Specific examples of the subphthalocyanine compound are shown below, but the present invention is not limited thereto. X⁻ is preferably selected from the counter anion X group which will be described later. Incidentally, formally, X⁻ is denoted independently, but X may be coordinated to a boron atom which forms subphthalocyanine.

Among the specific examples, (SP-2), (SP-3), (SP-4), (SP-5), (SP-6), and (SP-7) are particularly preferable from the viewpoints of color characteristics and heat resistance.

For D in General Formula (I) in the dye (A) according to the present invention, a hydrogen atom in the dye structure may be substituted with a substituent selected from the following substituent group A.

<<Squarylium Dye>>

As the squarylium dye used in the present invention, a dye represented by the following General Formula (K) is preferable.

In General Formula (K), A and B each independently represent an aryl group or a heterocyclic group. As the aryl group, an aryl group having 6 to 48 carbon atoms is preferable, an aryl group having 6 to 24 carbon atoms is more preferable, and examples thereof include phenyl and naphthyl. As the heterocyclic group, a heterocyclic group of a 5- or 6-membered ring is preferable, and examples thereof include pyrroyl, imidazoyl, pyrazoyl, thienyl, pyridyl, pyrimidyl, pyridazyl, triazol-1-yl, furyl, and thiadiazoyl.

As the compound represented by General Formula (K), a compound represented by the following General Formula (K-1), the following General Formula (K-2), the following General Formula (K-3), or the following General Formula (K-4) is particularly preferable.

In General Formula (K-1), R⁹¹, R⁹², R⁹⁴, R⁹⁵, R⁹⁶, and R⁹⁸ each independently represent a hydrogen atom, a halogen atom, a linear or branched alkyl group, a cycloalkyl group, a linear or branched alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group, an aryloxy group, a silyloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, an amino group (including an alkylamino group and an anilino group), an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, an alkylsulfonylamino or arylsulfonylamino group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, a sulfo group, an alkylsulfinyl or arylsulfinyl group, an alkylsulfonyl or arylsulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an arylazo group, a heterocyclic azo group, an imide group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, or a silyl group.

R⁹³ and R⁹⁷ each independently represent a hydrogen atom, a linear or branched alkyl group, a cycloalkyl group, a cycloalkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.

Each of R⁹¹ and R⁹², and R⁹⁵ and R⁹⁶ may be bonded to each other to form a ring.

The substituents which R⁹¹, R⁹², R⁹⁴, R⁹⁵, R⁹⁶, and R⁹⁸ in General Formula (K-1) can contain are the same as the substituents exemplified in the section of the substituent group A.

It is preferable that R⁹¹ to R⁹⁸ each independently represent a hydrogen atom, an alkyl group, a hydroxyl group, an amino group, an aryl group, or a heterocyclic group, it is more preferable that R⁹³, R⁹⁴, R⁹⁷, and R⁹⁸ each represent an alkyl group, and R⁹¹ and R⁹², and R⁹⁵ and R⁹⁶ are bonded to each other to form an aryl ring, and it is most preferable that R⁹³, R⁹⁴, R⁹⁷, and R⁹⁸ each represent an alkyl group having 1 to 20 carbon atoms, and R⁹¹ and R⁹², and R⁹⁵ and R⁹⁶ are bonded to each other to form a benzene ring.

In General Formula (K-2), R¹⁰¹, R¹⁰³, R¹⁰⁴, R¹⁰⁵, R¹⁰⁷, and R¹⁰⁸ each have the same definitions as R⁹¹, R⁹³, R⁹⁴, R⁹⁵, R⁹⁷, and R⁹⁸ in General Formula (K-1). R¹⁰³ and R¹⁰⁷ have the same definitions as R⁹³ and R⁹⁷ in General Formula (K-1).

In General Formula (K-2), it is preferable that R¹⁰¹, R¹⁰³, R¹⁰⁴, R¹⁰⁵, R¹⁰⁷, and R¹⁰⁸ are each a hydrogen atom, an alkyl group, a hydroxyl group, an amino group, an aryl group, or a heterocyclic group, it is more preferable that R¹⁰¹, R¹⁰³, R¹⁰⁵, and R¹⁰⁷ are each an alkyl group or an aryl group, and R¹⁰⁴ and R¹⁰⁸ are each a hydroxyl group or an amino group, and it is more preferable that R¹⁰¹, R¹⁰³, R¹⁰⁵, and R¹⁰⁷ are each an alkyl group having 1 to 20 carbon atoms, and R¹⁰⁴ and R¹⁰⁸ are each a hydroxyl group. R¹⁰³ and R¹⁰⁷ are preferably a hydrogen atom, a linear or branched alkyl group, or an aryl group, and more preferably an alkyl group having 1 to 5 carbon atoms and a phenyl group.

In General Formula (K-3), R¹⁰⁹, R¹¹⁰, R¹¹¹, R¹¹², R¹¹³, R¹¹⁴, R¹¹⁵, R¹¹⁸, and R¹¹⁹ have the same definitions as R⁹¹, R⁹³, R⁹⁴, R⁹⁵, R⁹⁷, and R⁹⁸ in General Formula (K-3). R¹¹⁶ and R¹¹⁷ have the same definitions as R⁹³ and R⁹⁷ in General Formula (K-1).

In General Formula (K-3), it is preferable that R¹⁰⁹, R¹¹⁰, R¹¹¹, R¹¹², R¹¹³, R¹¹⁴, R¹¹⁵, R¹¹⁸, and R¹¹⁹ are each a hydrogen atom, a halogen atom, a linear or branched alkyl group, a hydroxyl group, or an alkoxy group, and particularly, it is most preferable that R¹⁰⁹, R¹¹³, R¹¹⁵, R¹¹⁸, and R¹¹⁹ are each a hydrogen atom, and R¹¹⁰, R¹¹¹, and R¹¹² are each a hydrogen atom or an alkoxy group, and R¹¹⁴ is a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.

In General Formula (K-4), R¹²⁰ and R¹²¹ each independently represent a halogen atom, an alkyl group, an alkoxy group, or an alkenyl group. m1 and m2 each independently represent an integer of 1 to 4. n1 and n2 each independently represent an integer of 0 to 4.

R¹²⁰ and R¹²¹ are particularly preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. m1 and m2 are preferably 1 to 3, and most preferably 3. n1 and n2 are preferably 0 to 3, and preferably 0 or 1.

As the dye compound that can form a dye structure in the present invention, the squarylium compound represented by the General Formula (K-1) is preferable from the viewpoint of hue.

The squarylium compounds represented by General Formulae (K-1) to (K-4) can be synthesized by applying the method described in J. Chem. Soc., Perkin Trans. 1, 2000, 599.

Specific examples of the squarylium compounds represented by General Formulae (K-1) to (K-4) are shown below, but the present invention is not limited thereto.

Among the specific examples, (sq-1), (sq-2), (sq-3), (sq-7), (sq-8), (sq-9), (sq-9), (sq-10), (sq-11), and (sq-12) are preferable from the viewpoints of color characteristics and heat resistance.

<Substituent Group A>

Examples of the substituent which may be contained in the dye include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group, an aryloxy group, a silyloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, an amino group (including an alkylamino group and an anilino group), an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, an alkylsulfonylamino or arylsulfonylamino group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, a sulfo group, an alkylsulfinyl or arylsulfinyl group, an alkylsulfonyl or arylsulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an arylazo or heterocyclic azo group, an imide group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, and a silyl group. These will be described in detail below.

Examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a linear or branched alkyl group (a linear or branched substituted or unsubstituted alkyl group, and preferably an alkyl group having 1 to 30 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl, 2-chloroethyl, 2-cyanoethyl, and 2-ethylhexyl), a cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, for example, cyclohexyl and cyclopentyl, or a polycycloalkyl group, for example, a group having a polycyclic structure such as a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, for example, bicyclo[1,2,2]heptan-2-yl and bicyclo[2,2,2]octan-3-yl), and a tricycloalkyl group. Among these, a monocyclic cycloalkyl group and a bicycloalkyl group are preferable, and a monocyclic cycloalkyl group is particularly preferable),

a linear or branched alkenyl group (a linear or branched substituted or unsubstituted alkenyl group, which is preferably an alkenyl group having 2 to 30 carbon atoms, for example, vinyl, allyl, prenyl, geranyl, and oleyl), a cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, for example, 2-cyclopenten-1-yl and 2-cyclohexen-1-yl, a polycyclic alkenyl group, for example, a bicycloalkenyl group (preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, for example, bicyclo[2,2,1]hepto-2-en-1-yl and bicyclo[2,2,2]octo-2-en-4-yl), or a tricycloalkenyl group. Among these, a monocyclic cycloalkenyl group is particularly preferable), an alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, for example, an ethynyl group, a propargyl group, and a trimethylsilylethynyl group),

an aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, for example, phenyl, p-tolyl, naphthyl, m-chlorophenyl, and o-hexadecanoylaminophenyl), a heterocyclic group (preferably a substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, and monocyclic or ring-fused 5- to 7-membered heterocyclic group, more preferably a heterocyclic group of which ring-constituting atoms are selected from a carbon atom, a nitrogen atom, and a sulfur atom, and which has at least any one of hetero atoms including a nitrogen atom, an oxygen atom, and a sulfur atom, and still more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, for example, 2-furyl, 2-thienyl, 2-pyridyl, 4-pyridyl, 2-pyrimidinyl, and 2-benzothiazolyl), a cyano group, a hydroxyl group, a nitro group, a carboxyl group,

an alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, for example, methoxy, ethoxy, isopropoxy, tert-butoxy, n-octyloxy, and 2-methoxyethoxy), an aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, for example, phenoxy, 2-methylphenoxy, 2,4-di-tert-amylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy, and 2-tetradecanoylaminophenoxy), a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, for example, trimethylsilyloxy and tert-butyldimethylsilyloxy), a heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, with heterocyclic moiety being preferably the heterocyclic moiety explained for the aforementioned heterocyclic group and the heterocyclic oxy group being, for example, 1-phenyltetrazol-5-oxy or 2-tetrahydropyranyloxy),

an acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, and a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, for example, formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, and p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, for example, N,N-dimethylcarbamoyloxy, N,N-diethylcarbamoyloxy, morpholinocarbonyloxy, N,N-di-n-octylaminocarbonyloxy, and N-n-octylcarbamoyloxy), an alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, for example, methoxycarbonyloxy, ethoxycarbonyloxy, tert-butoxycarbonyloxy, and n-octylcarbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, for example, phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, and p-n-hexadecyloxyphenoxycarbonyloxy),

an amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, and a heterocyclic amino group having 0 to 30 carbon atoms, for example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, and N-1,3,5-triazin-2-ylamino), an acylamino group (preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, and a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, for example, formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, and 3,4,5-tri-n-octyloxyphenylcarbonylamino), an aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, for example, carbamoylamino, N,N-dimethylaminocarbonylamino, N,N-diethylaminocarbonylamino, and morpholinocarbonylamino), an alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, n-octadecyloxycarbonylamino, and N-methyl-methoxycarbonylamino),

an aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, for example, phenoxycarbonylamino, p-chlorophenoxycarbonylamino, and m-n-octyloxyphenoxycarbonylamino), a sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, for example, sulfamoylamino, N,N-dimethylaminosulfonylamino, and N-n-octylaminosulfonylamino), an alkylsulfonylamino or arylsulfonylamino group (preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, for example, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, and p-methylphenylsulfonylamino), a mercapto group,

an alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, for example, methylthio, ethylthio, and n-hexadecylthio), an arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, for example, phenylthio, p-chlorophenylthio, and m-methoxyphenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, in which a heterocyclic moiety is preferably the heterocyclic moiety explained for the aforementioned heterocyclic group, for example, 2-benzothiazolylthio and 1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfamoyl, N-(3-dodecyloxypropyl)sulfamoyl, N,N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, and N—(N′-phenylcarbamoyl)sulfamoyl), a sulfo group,

an alkylsulfinyl or arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms or a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, for example, methylsulfinyl, ethylsulfinyl, phenylsulfinyl, and p-methylphenylsulfinyl), an alkylsulfonyl or arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms or a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, for example, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, and p-methylphenylsulfonyl), an acyl group (preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, for example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, and p-n-octyloxyphenylcarbonyl), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, for example, phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, and p-tert-butylphenoxycarbonyl),

an alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, and n-octadecyloxycarbonyl), a carbamoyl group (preferably substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, for example, carbamoyl, N-methylcarbamoyl, N,N-dimethylcarbamoyl, N,N-di-n-octylcarbamoyl, and N-(methylsulfonyl)carbamoyl), an arylazo or heterocyclic azo group (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, or a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms (in which a heterocyclic moiety is preferably the heterocyclic moiety explained for the aforementioned heterocyclic group), for example, phenylazo, p-chlorophenylazo, and 5-ethylthio-1,3,4-thiadiazol-2-ylazo), an imide group (preferably a substituted or unsubstituted imide group having 2 to 30 carbon atoms, for example, N-succinimide and N-phthalimide), a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, for example, dimethylphosphino, diphenylphosphino, and methylphenoxyphosphino), a phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, for example, phosphinyl, dioctyloxyphosphinyl, and diethoxyphosphinyl),

a phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, for example, diphenoxyphosphinyloxy and dioctyloxyphosphinyloxy), a phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino and dimethylaminophosphinylamino), and a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, for example, trimethylsilyl, tert-butyldimethylsilyl, and phenyldimethylsilyl).

Among the above functional groups, in the functional groups having hydrogen atoms, the portion of hydrogen atoms in the functional groups may be substituted with any one of the above groups. Examples of the functional groups which can be introduced as substituents include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group, and specific examples thereof include a methylsulfonylaminocarbonyl group, a p-methylphenylsulfonylaminocarbonyl group, an acetylaminosulfonyl group, and a benzoylaminosulfonyl group.

<<Counter Anion>>

Examples of the counter anion which is preferably contained in the dye residue D in General Formula (I) are not particularly limited as long as they are counter anions, but are preferably non-nucleophilic anions from the viewpoint of heat resistance. As the non-nucleophilic counter anions, known non-nucleophilic anions described in paragraph “0075” of JP2007-310315A, and the like are preferable, and the following counter anion group X is more preferable:

a sulfonic acid anion, a carboxylic acid anion, a sulfonylimide anion, a bis(alkylsulfonyl)imide anion, a tris(alkylsulfonyl)methide anion, a carboxylic acid anion, a tetraarylborate anion, —CON⁻CO—, —CON⁻SO₂—, BF₄ ⁻, PF₆ ⁻, SbF₆ ⁻, and B⁻(CN)₃OMe.

As the counter anion group X, a sulfonic acid anion, a sulfonylimide anion, a bis(alkylsulfonyl)imide anion, a tris(alkylsulfonyl)methide anion, a carboxylic acid anion, a tetraarylborate anion, BF₄ ⁻, PF₆ ⁻, and SbF₆ ⁻ are still more preferable.

Among these, non-nucleophilic anions having structures represented by the following Formulae (AN-1) to (AN-5) are preferable as the counter anion group X.

(In Formula (AN-1), X¹ and X² each independently represent a fluorine atom or a fluorine atom-containing alkyl group having 1 to 10 carbon atoms, or X¹ and X² may be bonded to each other to form a ring.)

X¹ and X² are each preferably a perfluoroalkyl group having 1 to 10 carbon atoms, and more preferably a perfluoroalkyl group having 1 to 4 carbon atoms.

(In Formula (AN-2), X³, X⁴, and X⁵ each independently represent a fluorine atom, or a fluorine atom-containing alkyl group having 1 to 10 carbon atoms.)

X³, X⁴, and X⁵ are preferably a perfluoroalkyl group having 1 to 10 carbon atoms, and more preferably a perfluoroalkyl group having 1 to 4 carbon atoms. X⁶—SO₃ ⁻  (AN-3)

(In Formula (AN-3), X⁶ represents a fluorine atom-containing alkyl group having 1 to 10 carbon atoms.)

X⁶ is preferably a perfluoroalkyl group having 1 to 10 carbon atoms, and more preferably a perfluoroalkyl group having 1 to 4 carbon atoms. O₃ ⁻S—X⁷—SO₃ ⁻  (AN-4)

(In Formula (AN-4), X⁷ represents a fluorine atom-containing alkylene group having 1 to 10 carbon atoms.)

X⁷ is preferably a perfluoroalkylene group having 1 to 10 carbon atoms, and more preferably a perfluoroalkylene group having 1 to 4 carbon atoms.

(In Formula (AN-5), Ar¹, Ar², Ar³, and Ar⁴ represent an aryl group.)

The aryl group represented by Ar¹, Ar², Ar³, and Ar⁴ may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an aryl group, an alkoxy group, a carbonyl group, a carbonyloxy group, a carbamoyl group, a sulfo group, a sulfonamide group, and a nitro group, and in particular, a fluorine atom and an alkyl group are preferable, and a fluorine atom and a perfluoroalkyl group having 1 to 4 carbon atoms are more preferable.

Ar¹, Ar², Ar³, and Ar⁴ are preferably a phenyl group, a pentafluorophenyl group, or a 3,5-trifluorophenyl group, and most preferably a pentafluorophenyl group.

The mass per molecule of the non-nucleophilic counter anion used in the present invention is preferably 100 to 1000, and more preferably 200 to 800.

The dye of the present invention may include one kind or two or more kinds of non-nucleophilic counter anion.

Specific examples of the non-nucleophilic counter anion used in the present invention are shown below, but the present invention is not limited thereto.

<<<Polymerizable Group>>>

The dye residue D may have a polymerizable group.

As the polymerizable group, known polymerizable groups which can be crosslinked by a radical, an acid, or heat can be used, and examples thereof include a group having an ethylenically unsaturated bond, a cyclic ether group (an epoxy group or an oxetane group), and a methylol group. In particular, a group having an ethylenically unsaturated bond is preferable, a (meth)acryloyl group is more preferable, and a (meth)acryloyl group derived from glycidyl (meth)acrylate and 3,4-epoxy-cyclohexylmethyl (meth)acrylate is particularly preferable.

It is preferable that the number of the polymerizable groups in the dye residue D contained in one dye residue is 1.

<<Various Properties of Dye (A)>>

The Tg of the dye (A) according to the present invention is preferably 50° C. or higher, and more preferably 100° C. or higher. Further, a 5% weight reduction temperature measured by thermogravimetric analysis (TGA measurement) is preferably 120° C. or higher, more preferably 150° C. or higher, and still more preferably 200° C. or higher. If the temperature is within this range, when the coloring composition of the present invention is applied to the manufacture of a color filter or the like, change in the concentration caused by a heating process can be decreased.

In addition, the absorption coefficient (hereinafter described as ε′. ε′=ε/average molecular weight, unit: L/g·cm) per unit weight of the dye according to the present invention is preferably 30 or more, more preferably 60 or more, and still more preferably 100 or more. If the absorption coefficient is within this range, in the case where a color filter is manufactured using the coloring composition of the present invention, a color filter having excellent color reproducibility can be manufactured.

The molar absorption coefficient of the dye (A) used in the coloring composition of the present invention is preferably as high as possible from the viewpoint of coloring ability.

The molecular weight of the dye (A) is preferably 500 to 10000, more preferably 1000 to 8000, and still more preferably 2000 to 6000. In the case where the dye (A) in the coloring composition of the present invention is a mixture, the molecular weight dispersity is preferably 1.00 to 2.00, more preferably 1.00 to 1.50, and still more preferably 1.00 to 1.20. By setting the molecular weight distribution within the above range, the deviation in molecular weight is decreased, and the pattern properties are improved. The molecular weight distribution can be measured by, for example, gel permeation chromatography (GPC), or the like.

The dye (A) preferably has an acid group or a polymerizable group in R in General Formula (I) as described above, but even in the case where a portion (for example, Q or D) in the oligomer molecule, other than R, contains an acid group or a polymerizable group, the same effects as in a case where an acid group or a polymerizable group is contained in R are exerted.

In the present invention, it is preferable that at least one selected from the linking group Q, the substituent R, and the dye residue D of General Formula (I) contains an acid group. As the acid group, a carboxyl group, a sulfo group, or a phosphoric acid group is preferable, and a carboxyl group is more preferable.

In the present invention, the number of the polymerizable groups contained in the entire dye (A) is preferably 1 to 2, and more preferably 1. Further, the number of the acid groups contained in the entire dye (A) is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 to 2.

The acid value of the dye (A) is not particularly limited, but is preferably 0.1 mmol/g to 1.0 mmol/g, more preferably 0.2 mmol/g to 1.0 mmol/g, and still more preferably 0.2 mmol/g to 0.7 mmol/g. If the acid value is 0.1 mmol/g or more, the developability can be further improved. Further, if the acid value is 1.0 mmol or less, it is possible to form a cured film which is difficult to be decolored by a developing liquid, a peeling solution, or the like.

The C═C value of the dye (A) is preferably 0.1 mmol/g or more, more preferably 0.2 mmol/g or more, and still more preferably 0.3 mmol/g or more. If the C═C value is 0.1 mmol/g or more, it is possible to form a cured film which is difficult to be decolored by a developing liquid, a peeling solution, or the like. The upper limit in the C═C values is not particularly limited, but is preferably, for example, 1.0 mmol/g, and more preferably 0.70 mmol/g. The C═C value can be calculated by dividing the number of the polymerizable groups introduced into the dye (A) with the molecular weight of the dye (A), or can also be measured by an analysis means such as ¹H-NMR.

The dye (A) according to the present invention is preferably a dye. The dye refers to a dye having a substantial solubility in water or an organic solvent, and in particular, it is preferably an organic solvent-soluble dye, which is dissolved in the following organic solvent.

Examples of the organic solvent include esters (for example, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, butyl acetate, and methyl 3-methoxypropionate), ethers (for example, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate), ketones (methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone), and aromatic hydrocarbons (for example, toluene and xylene). The dye (A) dissolves in the amount of preferably 1% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and still more preferably 10% by mass to 30% by mass, with respect to these solvents. If the solubility is within this range, when the coloring composition of the present invention is applied to the manufacture of a color filter or the like, a suitable coating surface or suppressed reduction in the concentration due to elution after coating in other colors can be obtained.

In the coloring composition of the present invention, the dye (A) may be used alone or in combination of two or more kinds thereof.

The content of the dye (A) in the coloring composition of the present invention is determined in consideration of its content ratio to a pigment (C) which will be described later.

The mass ratio of the dye to the pigment (dye (A)/pigment) is preferably 0.1 to 5, more preferably 0.2 to 2, and still more preferably 0.3 to 1.

The content of the dye in the coloring composition of the present invention is preferably 1.0% by mass to 50% by mass, more preferably 5.0% by mass to 30% by mass, and particularly preferably 10% by mass to 25% by mass, with respect to the total solid content in the coloring composition.

Specific examples of the dye used in the coloring composition of the present invention include the compounds shown in Examples which will be described later. It is needless to say that the present invention is not limited thereto.

The coloring composition of the present invention may include known dyes (A) other than the dye represented by General Formula (I). For example, dyes disclosed in JP1989-90403A (JP-564-90403A), JP1989-91102A (JP-564-91102A), JP1989-94301A (JP-H01-94301A), JP1994-11614A (JP-H06-11614A), JP2592207B, U.S. Pat. Nos. 4,808,501A, 5,667,920A, 505,950A, 5,667,920A, JP1993-333207A (JP-H05-333207A), JP1994-35183A (JP-H06-35183A), JP1994-51115A (JP-H06-51115A), and JP1994-194828A (JP-H06-194828A) can be used. With respect to the chemical structure, dyes such as a pyrazoleazo-based dye, a pyrromethene-based dye, an anilinoazo-based dye, a triphenylmethane-based dye, an anthraquinone-based dye, a benzylidene-based dye, an oxonol-based dye, a pyrazoletriazole azo-based dye, a pyridoneazo-based dye, a cyanine-based dye, a phenothiazine-based dye, and a pyrrolopyrazoleazomethine-based dye can be used.

<Polymerizable Compound (B)>

The coloring composition of the present invention contains a polymerizable compound. As the polymerizable compound, known polymerizable compounds which can be crosslinked by a radical, an acid, or heat can be used. Examples thereof include polymerizable compounds having an ethylenically unsaturated bond, a cyclic ether (epoxy or oxetane), methylol, or the like. From the viewpoint of sensitivity, the polymerizable compound is suitably selected from compounds having at least one and preferably two or more terminal ethylenically unsaturated bonds. Among these, polyfunctional polymerizable compounds having 4 or more functional groups are preferable, and polyfunctional polymerizable compounds having 5 or more functional groups are more preferable. Further, an alkali-soluble resin having a polymerizable group, which will be described later, can also be used as a polymerizable compound.

Such compound groups are widely known in the industrial field of the relevant art and can be used in the present invention without particular limitation. These may be in any type of chemical forms such as a monomer, a prepolymer, that is, a dimer, a trimer, an oligomer, a mixture thereof, and an oligomer thereof. The polymerizable compound in the present invention may be used alone or in combination of two or more kinds thereof.

More specifically, examples of the monomer and prepolymer include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, and the like) or esters thereof, amides, and multimers of these, and among these, an ester of unsaturated carboxylic acid and an aliphatic polyol compound, amides of unsaturated carboxylic acid and an aliphatic polyamine compound, and multimers of these are preferable. Moreover, products of an addition reaction between unsaturated carboxylic acid esters or amides having nucleophilic substituent such as a hydroxyl group, an amino group, or a mercapto group and monofunctional or polyfunctional isocyanates or epoxies, products of a dehydration condensation reaction between the unsaturated carboxylic acid esters or amides and a monofunctional or polyfunctional carboxylic acid, and the like are also suitably used. In addition, products of an addition reaction between unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group and monofunctional or polyfunctional alcohols, amines, or thiols, and products of a substitution reaction between unsaturated carboxylic acid esters or amides having an eliminatable substituent such as a halogen group or tosyloxy group and monofunctional or polyfunctional alcohols, amines, or thiols are also suitable. As other examples, instead of the above unsaturated carboxylic acid, vinyl benzene derivatives of unsaturated phosphonic acid, styrene, and the like and compound groups substituted with vinyl ether, allyl ether, or the like can also be used.

As these specific compounds, the compounds described in paragraph Nos. “0095” to “0108” of JP2009-288705A can also be suitably used in the present invention.

Moreover, as the polymerizable compound, a compound which has at least one addition-polymerizable ethylene group and has an ethylenically unsaturated group having a boiling point of 100° C. or higher under normal pressure is also preferable. Examples of the compound include a monofunctional acrylate or methacrylate such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate; a compound which is obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol, and then (meth)acrylating the resultant, such as polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol (meth)acrylate, trimethylolpropane tri(acryloyloxypropyl)ether, tri(acryloyloxyethyl) isocyanurate, glycerin, and trimethylolethane, the urethane (meth)acrylates described in JP1973-41708B (JP-S48-41708B), JP1975-6034B (JP-S50-6034B), and JP1976-37193A (JP-S51-37193A), the polyester acrylates described in JP1973-64183A (JP-S48-64183A), JP1974-43191B (JP-S49-43191B), and JP1977-30490B (JP-S52-30490B), a polyfunctional acrylate or methacrylate such as epoxy acrylate as a product of a reaction between an epoxy resin and a (meth)acrylic acid, and a mixture thereof.

Other examples thereof include a polyfunctional (meth)acrylate which is obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth)acrylate, and an ethylenically unsaturated group.

Furthermore, as other preferred polymerizable compounds, the compounds having a fluorene ring and an ethylenically unsaturated group having 2 or more functional groups described in JP2010-160418A, JP2010-129825A, and JP4364216B, and a cardo resin can also be used.

Moreover, as the compound which has a boiling point of 100° C. or higher under normal pressure and has at least one addition-polymerizable ethylenically unsaturated group, compounds described in paragraph Nos. “0254” to “0257” of JP2008-292970A are also suitable.

In addition to those above, radically polymerizable monomers represented by the following General Formulae (MO-1) to (MO-5) can also be suitably used. Incidentally, in the case where T is an oxyalkylene group in the formulae, the terminal on a carbon atom side binds to R.

In General Formulae, n is 0 to 14, and m is 1 to 8. A plurality of R's and T's which are present in the same molecule may be the same as or different from each other.

In each of the polymerizable compounds represented by General Formulae (MO-1) to (MO-5), at least one of the plurality of R's represents a group represented by —OC(═O)CH═CH₂ or —OC(═O)C(CH₃)═CH₂.

As specific examples of the polymerizable compounds represented by General Formulae (MO-1) to (MO-5), the compounds described in paragraph Nos. “0248” to “0251” of JP2007-269779A can also be suitably used in the present invention.

In addition, a compound which is obtained by adding ethylene oxide or propylene oxide to the polyfunctional alcohol, which is described as General Formulae (1) and (2) in JP1998-62986A (JP-H10-62986A) together with the specific examples thereof, and then (meth)acrylating the resultant can also be used as a polymerizable compound.

Among these, as the polymerizable compound, dipentaerythritol triacrylate (KAYARAD D-330 as a commercially available product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercially available product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (KAYARAD D-310 as a commercially available product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (KAYARAD DPHA as a commercially available product; manufactured by Nippon Kayaku Co., Ltd.), and a structure in which ethylene glycol or a propylene glycol residue is interposed between these (meth)acryloyl groups is preferable. Oligomer types of these can also be used. Preferred embodiments of the polymerizable compound are shown below.

The polymerizable compound is a polyfunctional monomer and may have an acid group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. If an ethylenic compound has an unreacted carboxyl group as in a case where the ethylene compound is a mixture described above, this compound can be used as is, but if desired, a hydroxyl group of the aforementioned ethylenic compound may be reacted with a non-aromatic carboxylic anhydride so as to introduce an acid group. In this case, specific examples of the non-aromatic carboxylic anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride.

In the present invention, as a monomer having an acid group, a polyfunctional monomer which is an ester obtained between an aliphatic polyhydroxy compound and an unsaturated carboxylic acid and provides an acid group by reacting an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride is preferable. A monomer in which the aliphatic polyhydroxy compound in the ester is pentaerythritol and/or dipentaerythritol is particularly preferable. Examples of commercially available products thereof include M-510 and M-520, which are polybasic modified acryl oligomers manufactured by TOAGOSEI, CO., LTD.

These monomers may be used alone, but since it is difficult to use a single compound in production, two or more kinds thereof may be used as a mixture. Moreover, if desired, a polyfunctional monomer not having an acid group and a polyfunctional monomer having an acid group may be used in combination therewith as the monomer.

The acid value of the polyfunctional monomer having an acid group is preferably 0.1 mgKOH/g to 40 mgKOH/g, and particularly preferably 5 mgKOH/g to 30 mgKOH/g. If the acid value of the polyfunctional monomer is too low, the development solubility characteristics deteriorates. If the acid value is too high, difficulty is caused in the production and handleability, hence a photopolymerization performance deteriorates, which leads to deterioration of curability such as surface smoothness of pixels. Therefore, in the case where a combination of two or more kinds of polyfunctional monomers having different acid groups is used, or when a combination of polyfunctional monomers not having an acid group is used, it is preferable to adjust the acid value such that the acid value of all the polyfunctional monomers falls within the above range.

Furthermore, it is also a preferred embodiment that a polyfunctional monomer having a caprolactone structure is contained as a polymerizable monomer.

The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in a molecule thereof, and examples thereof include ε-caprolactone-modified polyfunctional (meth)acrylates which are obtained by esterifying polyols such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, and trimethylolmelamine with (meth)acrylic acid and ε-caprolactone. Among these, a polyfunctional monomer having a caprolactone structure represented by the following General Formula (Z-1) is preferable.

In General Formula (Z-1), all of six R's are each a group represented by the following General Formula (Z-2). Alternatively, one to five out of six R's are a group represented by the following General Formula (Z-2), and the remainder is a group represented by the following General Formula (Z-3).

In General Formula (Z-2), R¹ represents a hydrogen atom or a methyl group, m represents a number 1 or 2, and “*” represents a direct bond.

In General Formula (Z-3), R¹ represents a hydrogen atom or a methyl group, and “*” represents a direct bond.

The polyfunctional monomer having such a caprolactone structure is commercially available from Nippon Kayaku Co., Ltd., as a KAYARAD DPCA series, and examples thereof include DPCA-20 (a compound in which m=1 in Formulae (1) to (3), the number of the group represented by Formula (2)=2, and all of R¹'s are hydrogen atoms), DPCA-30 (a compound in which m=1 in Formulae (1) to (3), the number of the group represented by Formula (2)=3, and all of R¹'s are hydrogen atoms), DPCA-60 (a compound in which m=1 in Formulae (1) to (3), the number of the group represented by Formula (2)=6, and all of R¹'s are hydrogen atoms), and DPCA-120 (a compound in which m=2 in Formulae (1) to (3), the number of the group represented by Formula (2)=6, and all of R¹'s are hydrogen atoms).

In the present invention, the polyfunctional monomer having a caprolactone structure can be used alone or as a mixture of two or more kinds thereof.

Moreover, the specific monomer in the present invention is preferably at least one kind selected from a group of compounds represented by the following General Formula (Z-4) or (Z-5).

In General Formulae (Z-4) and (Z-5), E's each independently represent —((CH₂)_(y)CH₂O)— or —((CH₂)_(y)CH(CH₃)O)—, y's each independently represent an integer of 0 to 10, and X's each independently represent an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.

In General Formula (Z-4), the sum of the acryloyl group and the methacryloyl group is 3 or 4, m's each independently represent an integer of 0 to 10, and the sum of the respective m's is an integer of 0 to 40. Here, in the case where the sum of the respective m's is 0, any one of X's is a carboxyl group.

In General Formula (Z-5), the sum of the acryloyl group and the methacryloyl group is 5 or 6, n's each independently represent an integer of 0 to 10, and the sum of the respective n's is an integer of 0 to 60. Here, in the case where the sum of the respective n's is 0, one of X's is a carboxyl group.

In General Formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.

Moreover, the sum of the respective m's is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.

In General Formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.

Furthermore, the sum of the respective n's is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.

In addition, —((CH₂)_(y)CH₂O)— or —((CH₂)_(y)CH(CH₃)O)— in General Formula (Z-4) or (Z-5) is preferably in the form in which the terminal on an oxygen atom side binds to X.

The compound represented by General Formula (Z-4) or (Z-5) may be used alone or in combination of two or more kinds thereof. In particular, a form in which all of six X's in General Formula (Z-5) are an acryloyl group is preferable.

Moreover, the total content of the compound represented by General Formula (Z-4) or (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.

The compound represented by General Formula (Z-4) or (Z-5) can be synthesized by steps known in the related art, which includes a step of binding ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol by a ring-opening addition reaction to form a ring-opening skeleton, and a step of reacting, for example, (meth)acryloyl chloride to a terminal hydroxyl group of the ring-opening skeleton to introduce a (meth)acryloyl group. Since the respective steps are well-known, a person skilled in the art can easily synthesize the compound represented by General Formula (Z-4) or (Z-5).

Among the compounds represented by General Formula (Z-4) or (Z-5), a pentaerythritol derivative and/or a dipentaerythritol derivative is/are more preferable.

Specific examples of the compounds include compounds represented by the following Formulae (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”). Among these, the exemplary compounds (a), (b), (e), and (f) are preferable.

Examples of commercially available products of the polymerizable compounds represented by General Formulae (Z-4) and (Z-5) include SR-494 which is a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer Company, Inc., and DPCA-60 which is a hexafunctional acrylate having six pentyleneoxy chains and TPA-330 which is a trifunctional acrylate having three isobutyleneoxy chains, manufactured by Nippon Kayaku Co., Ltd.

Moreover, as the polymerizable compounds, the urethane acrylates described in JP1973-41708B (JP-S48-41708B), JP1976-37193A (JP-S51-37193A), JP1990-32293B (JP-H02-32293B), and JP1990-16765B (JP-H02-16765B) or urethane compounds having an ethylene oxide-based skeleton described in JP1983-49860B (JP-S58-49860B), JP1981-17654B (JP-S56-17654B), JP1987-39417B (JP-S62-39417B), and JP1987-39418B (JP-S62-39418B) are also preferable. Furthermore, if addition-polymerizable compounds, which have an amino structure or a sulfide structure in a molecule and are described in JP1988-277653A (JP-S63-277653A), JP1988-260909A (JP-S63-260909A), and JP1989-105238A (JP-H01-105238A), are used as the polymerizable compounds, a curable composition which is extremely excellent in photosensitization speed can be obtained.

Examples of commercially available products of the polymerizable compounds include urethane oligomers UAS-10 and UAB-140 (manufactured by Sanyo-Kokusaku Pulp, Co., Ltd.), UA-7200 (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), and UA-306H, UA-306T, UA-3061, AH-600, T-600, and AI-600 (manufactured by KYOEISHA CHEMICAL Co., Ltd.).

As the cyclic ether (epoxy or oxethane), examples of a bisphenol A type epoxy resin, which have an epoxy group, include JER-827, JER-828, JER-834, JER-1001, JER-1002, JER-1003, JER-1055, JER-1007, JER-1009, and JER-1010 (all manufactured by Japan Epoxy Resins Co., Ltd.), and EPICLON 860, EPICLON 1050, EPICLON 1051, and EPICLON 1055 (all manufactured by DIC Corporation); examples of a bisphenol F type epoxy resin include JER-806, JER-807, JER-4004, JER-4005, JER-4007, and JER-4010 (all manufactured by Japan Epoxy Resins Co., Ltd.), EPICLON 830 and EPICLON 835 (both manufactured by DIC Corporation), and LCE-21 and RE-602S (all manufactured by Nippon Kayaku Co., Ltd.); examples of a phenol novolac type epoxy resin include JER-152, JER-154, JER-157S70, and JER-157S65 (all manufactured by Japan Epoxy Resins Co., Ltd.), and EPICLON N-740, EPICLON N-770, and EPICLON N-775 (all manufactured by DIC Corporation); examples of a cresol novolac type epoxy resin include EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, and EPICLON N-695 (all manufactured by DIC Corporation), and EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.); and examples of an aliphatic epoxy resin include ADEKA RESIN EP-40805, ADEKA RESIN EP-40855, and ADEKA RESIN EP-40885 (all manufactured by ADEKA CORPORATION), CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2083, CELLOXIDE 2085, EHPE-3150 (a 1,2-epoxy-4-(2-oxylanyl(cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol), EPOLEAD PB 3600, and EPOLEAD PB 4700 (all manufactured by Daicel Corporation), DENACOL EX-211L, EX-212L, EX-214L, EX-216L, EX-321L, and EX-850L (all manufactured by Nagase ChemteX Corporation), ADEKA RESIN EP-40005, ADEKA RESIN EP-40035, ADEKA RESIN EP-40105, and ADEKA RESIN EP-40115 (all manufactured by ADEKA CORPORATION), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, and EPPN-502 (all manufactured by ADEKA CORPORATION), and JER-10315 (manufactured by Japan Epoxy Resins Co., Ltd.). Such polymerizable compounds are suitable for a case of forming a pattern by a dry etching method.

Details of how to use these polymerizable compounds, such as the structure, whether the polymerizable compounds are used singly or used in combination thereof, and the amount of the polymerizable compounds added, can be arbitrarily set according to the designed final performance of the coloring composition. For example, from the viewpoint of sensitivity, a structure in which the content of an unsaturated group per molecule is large is preferable, and in many cases, it is preferable that the polymerizable compound has 2 or more functional groups. Moreover, from the viewpoint of enhancing the strength of a cured film formed of the coloring composition, it is preferable that the polymerizable compound has 3 or more functional groups. In addition, a method for adjusting both the sensitivity and the strength by using a combination of compounds which differ in the number of functional groups and have different polymerizable groups (for example, an acrylic acid ester, a methacrylic acid ester, a styrene-based compound, and a vinylether-based compound) is also effective. Further, it is preferable to use a combination of compounds having 3 or more functional groups and differing in the length of an ethylene oxide chain since the developability of the coloring composition can be adjusted, and excellent pattern formability is obtained.

In addition, from the viewpoints of the compatibility with other components (for example, a photopolymerization initiator, a substance to be dispersed, and an alkali-soluble resin) contained in the coloring composition, and the dispersibility, how to select and use the polymerizable compound is an important factor. For example, if a low-purity compound is used or a combination of two or more kinds thereof is used, the compatibility can be improved in some cases. In addition, there are also cases where specific structures are selected from the viewpoint of improving the adhesiveness to a hard surface of a support or the like.

The content of the polymerizable compound in the coloring composition of the present invention is preferably 0.1% by mass to 90% by mass, more preferably 1.0% by mass to 50% by mass, and particularly preferably 2.0% by mass to 30% by mass, with respect to the total solid contents of the coloring composition.

<Polyfunctional Thiol Compound>

The coloring composition of the present invention may contain polyfunctional thiol compounds having two or more mercapto groups in a molecule thereof for the purpose of promoting the reaction of the polymerizable compounds. The polyfunctional thiol compounds are preferably secondary alkanethiols, and particularly preferably compounds having structures represented by the following General Formula (T1).

(In Formula (T1), n represents an integer of 2 to 4, and L represents a divalent to tetravalent linking group.)

In General Formula (T1), it is preferable that the linking group L is an aliphatic group having 2 to 12 carbon atoms, and it is particularly preferable that n is 2 and L is an alkylene group having 2 to 12 carbon atoms. Specific examples of the polyfunctional thiol compound are compounds represented by the following Structural Formulae (T2) to (T4), and a compound represented by Formula (T2) is particularly preferable. These polyfunctional thiols can be used alone or in combination of multiple kinds thereof.

The amount of the polyfunctional thiol compound blended into the coloring composition of the present invention is preferably 0.3% by mass to 8.9% by mass, and more preferably 0.8% by mass to 6.4% by mass, based on the total solid content excluding the solvent. Further, the polyfunctional thiol may also be added for the purpose of improving stability, odor, resolution, developability, adhesiveness, or the like.

<Pigment (C)>

It is preferable that the coloring composition of the present invention contains a pigment.

As the pigment, various inorganic or organic pigments known in the related art can be used, and as the pigment, one having a high transmittance is preferable.

Examples of the inorganic pigment include black pigments such as carbon black and titanium black, metal compounds represented by a metal oxide, a metal complex salt, or the like, and specific examples thereof include metal oxides of iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and the like, and complex oxides of metals.

Examples of the organic pigment include:

-   -   C. I. Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110,         138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199;     -   C. I. Pigment Orange 36, 38, 43, 71;     -   C. I. Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176,         177, 209, 220, 224, 242, 254, 255, 264, 270;     -   C. I. Pigment Violet 19, 23, 32, 39;     -   C. I. Pigment Blue 1, 2, 15, 15:1, 15:3, 15:6, 16, 22, 60, 66;     -   C. I. Pigment Green 7, 36, 37, 58;     -   C. I. Pigment Brown 25, 28; and     -   C. I. Pigment Black 1.

Examples of the pigment which can be preferably used in the present invention include the following ones, but the present invention is not limited thereto.

C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,

-   -   C. I. Pigment Orange 36, 71,     -   C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254,         255, 264,     -   C. I. Pigment Violet 19, 23, 32,     -   C. I. Pigment Blue 15:1, 15:3, 15:6, 16, 22, 60, 66,     -   C. I. Pigment Green 7, 36, 37, 58, and     -   C. I. Pigment Black 1.

These organic pigments can be used alone or in various combinations for spectral adjustment or improvement of color purity. Specific examples of the combination are shown below. For example, as a red pigment, an anthraquinone-based pigment, a perylene-based pigment, or a diketopyrrolopyrrole-based pigment can be used alone or as a mixture of at least one kind of these with a disazo-based yellow pigment, an isoindoline-based yellow pigment, a quinophthalone-based yellow pigment, or a perylene-based red pigment. Examples of the anthraquinone-based pigment include C. I. Pigment Red 177, examples of the perylene-based pigment include C. I. Pigment Red 155, and C. I. Pigment Red 224, and examples of the diketopyrrolopyrrole-based pigment include C. I. Pigment Red 254. In view of chromatic resolving properties, a mixture of the above pigment with C. I. Pigment Yellow 139 is preferable. The mass ratio between the red pigment and the yellow pigment is preferably 100:5 to 100:50. If the mass ratio is 100:4 or less, it is difficult to reduce the light transmittance at 400 nm to 500 nm, and if it is 100:51 or more, a dominant wavelength moves closer to a short wavelength, so a color separating power cannot be improved in some cases. In particular, the mass ratio is optimally in a range of 100:10 to 100:30. Moreover, in a case of a combination of red pigments, the mass ratio can be adjusted according to the required spectrum.

In addition, as a green pigment, a halogenated phthalocyanine-based pigment can be used alone or as a mixture of this pigment with a disazo-based yellow pigment, a quinophthalone-based yellow pigment, an azomethine-based yellow pigment, or an isoindoline-based yellow pigment. As an example of such pigments, a mixture of C. I. Pigment Green 7, 36, or 37 with C. I. Pigment Yellow 83, C. I. Pigment Yellow 138, C. I. Pigment Yellow 139, C. I. Pigment Yellow 150, C. I. Pigment Yellow 180, or C. I. Pigment Yellow 185 is preferable. The mass ratio between the green pigment and the yellow pigment is preferably 100:5 to 100:150. The mass ratio is particularly preferably in a range of 100:30 to 100:120.

As a blue pigment, a phthalocyanine-based pigment can be used alone or as a mixture of this pigment with a dioxazine-based violet pigment. For example, a mixture of C. I. Pigment Blue 15:6 with C. I. Pigment Violet 23 is preferable. The mass ratio between the blue pigment and the violet pigment is preferably 100:0 to 100:100 and more preferably 100:10 or less.

Moreover, as a pigment for a black matrix, carbon, titanium black, iron oxide, or titanium oxide may be used alone or as a mixture, and a combination of carbon with titanium black is preferable. The mass ratio between carbon and titanium black is preferably in a range of 100:0 to 100:60.

In the case where the coloring composition is used for a color filter, the primary particle size of the pigment is preferably 100 nm or less from the viewpoint of color unevenness or contrast. From the viewpoint of dispersion stability, the primary particle size is preferably 5 nm or more. The primary particle size of the pigment is more preferably 5 nm to 75 nm, still more preferably 5 nm to 55 nm, and particularly preferably 5 nm to 35 nm. The specific dispersion resin according to the present invention can exert excellent effects particularly when it is combined with a pigment of which the primary particle size is in a range of 5 nm to 35 nm.

The primary particle size of the pigment can be measured by a known method such as electron microscopy.

Among these, the pigment is preferably a pigment selected from an anthraquinone pigment, a diketopyrrolopyrrole pigment, a phthalocyanine pigment, a quinophthalone pigment, an isoindoline pigment, an azomethine pigment, and a dioxazine pigment. In particular, C. I. Pigment Red 177 (anthraquinone pigment), C. I. Pigment Red 254 (diketopyrrolopyrrole pigment), C. I. Pigment Green 7, 36, 58, C. I. Pigment Blue 15:6 (phthalocyanine pigment), C. I. Pigment Yellow 138 (quinophthalone pigment), C. I. Pigment Yellow 139, 185 (isoindoline pigments), C. I. Pigment Yellow 150 (azomethine pigment), and C. I. Pigment Violet 23 (dioxazine pigment) are most preferable.

In the case where a pigment is blended into the coloring composition of the present invention, the content of the pigment is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, and still more preferably 30% by mass to 60% by mass, with respect to the total amount of components excluding a solvent, contained in the coloring composition.

—Pigment Dispersant—

In the case where the coloring composition of the present invention has a pigment, a pigment dispersant can be used in combination with other components, as desired.

Examples of the pigment dispersant include polymer dispersants [for example, a polyamide amine and a salt thereof, a polycarboxylic acid and a salt thereof, a high-molecular-weight unsaturated acid ester, a modified polyurethane, a modified polyester, a modified poly(meth)acrylate, a (meth)acrylic copolymer, and a naphthalene sulfonate formalin condensate], surfactants such as a polyoxyethylene alkyl phosphoric acid ester, a polyoxyethylene alkylamine, and a alkanolamine; and pigment derivatives.

The polymer dispersants can be further classified into straight-chain polymers, terminal-modified polymers, graft polymers, and block polymers, according to the structure.

Examples of the terminal-modified polymers which have a moiety anchored to the pigment surface include a polymer having a phosphoric acid group in the terminal as described in JP1991-112992A (JP-H03-112992A), JP2003-533455A, and the like, a polymer having a sulfonic acid group in the terminal as described in JP2002-273191A, a polymer having a partial skeleton or a heterocycle of an organic dye as described in JP1997-77994A (JP-H09-77994A), and the like. Moreover, a polymer obtained by introducing two or more moieties (acid groups, basic groups, partial skeletons of an organic dye, or heterocycles) anchored to the pigment surface into a polymer terminal as described in JP2007-277514A is also preferable since this polymer is excellent in dispersion stability.

Examples of the graft polymers having a moiety anchored to the pigment surface include polyester-based dispersant and the like, and specific examples thereof include a product of a reaction between a poly(lower alkyleneimine) and a polyester, which is described in JP1979-37082A (JP-S54-37082A), JP1996-507960A (JP-H08-507960A), JP2009-258668A, and the like, a product of a reaction between a polyallylamine and a polyester, which is described in JP1997-169821A (JP-H09-169821A) and the like, a copolymer of a macromonomer and a nitrogen atom monomer, which is described in JP1998-339949A (JP-H10-339949A), JP2004-37986A, WO2010/110491A, and the like, a graft polymer having a partial skeleton or a heterocycle of an organic dye, which is described in JP2003-238837A, JP2008-9426A, JP2008-81732A, and the like, and a copolymer of a macromonomer and an acid group-containing monomer, which is described in JP2010-106268A, and the like. From the viewpoint of dispersibility of a pigment dispersion, dispersion stability, and developability which a coloring composition using the pigment exhibits, an amphoteric dispersion resin having basic and acid groups, which is described in JP2009-203462A, is particularly preferable.

As the macromonomer used in production of a graft polymer having a moiety anchored to the pigment surface by radical polymerization, known macromonomers can be used. Examples thereof include macromonomers AA-6 (polymethyl methacrylate having a methacryloyl group as a terminal group), AS-6 (polystyrene having a methacryloyl group as a terminal group), AN-6S (a copolymer of styrene and acrylonitrile which has a methacryloyl group as a terminal group), and AB-6 (polybutyl acrylate having a methacryloyl group as a terminal group) manufactured by TOAGOSEI, CO., LTD.; Placcel FM5 (a product obtained by adding 5 molar equivalents of ε-caprolactone to 2-hydroxyethyl methacrylate) and FA10L (a product obtained by adding 10 molar equivalents of ε-caprolactone to 2-hydroxyethyl acrylate) manufactured by Daicel Corporation; a polyester-based macromonomer described in JP1990-272009A (JP-H02-272009A), and the like. Among these, from the viewpoint of dispersibility of the pigment dispersion, dispersion stability, and the developability which the coloring composition using the pigment dispersion exhibits, the polyester-based macromonomer excellent in flexibility and solvent compatibility is particularly preferable. Further, a polyester-based macromonomer represented by the polyester-based macromonomer described in JP1990-272009A (JP-H02-272009A) is most preferable.

As the block polymer having a moiety anchored to the pigment surface, block polymers described in JP2003-49110A, JP2009-52010A, and the like are preferable.

Other pigment dispersants which can be used in the present invention can be obtained in the form of commercially available products, and specific examples thereof include “DA-7301” manufactured by Kusumoto Chemicals, Ltd., “Disperbyk-101 (polyamidamine phosphate), 107 (carboxylic acid ester), 110 (copolymer including an acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, and 170 (polymeric copolymer)”, and “BYK-P104 and P105 (high-molecular-weight unsaturated polycarboxylic acid)”, manufactured by BYK-Chemie, “EFKA 4047, 4010 to 4050, 4050 to 4165 (polyurethane-based), EFKA 4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high-molecular-weight polycarboxylic acid salt), 6220 (aliphatic polyester), 6745 (phthalocyanine derivative), and 6750 (azo pigment derivative)” manufactured by EFKA, “Ajisper PB821, PB822, PB880, and PB881” manufactured by Ajinomoto Fine-Techno Co., Inc., “Flowlen TG-710 (urethane oligomer)” and “Polyflow No. 50E, No. 300 (acrylic copolymer)” manufactured by KYOEISHA CHEMICAL Co., LTD., “Disparlon KS-860, 873SN, 874, #2150 (aliphatic polyvalent carboxylic acid), #7004 (polyether ester), DA-703-50, DA-705, and DA-725”, manufactured by Kusumoto Chemicals, Ltd., “Demol RN, N (naphthalene sulfonate formaldehyde condensate), MS, C, SN—B (aromatic sulfonate formaldehyde condensate)”, “Homogenol L-18 (polymeric polycarboxylic acid)”, “Emulgen 920, 930, 935, and 985 (polyoxyethylene nonyl phenyl ether)”, and “Acetamine 86 (stearylamine acetate)”, manufactured by Kao Corporation, “Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, and 27000 (polymers having a functional portion in the terminal portion), and 24000, 28000, 32000, and 38500 (graft polymers)”, manufactured by The Lubrizol Corporation, “Nikkol T106 (polyoxyethylene sorbitan monooleate) and MYS-IEX (polyoxyethylene monostearate)” manufactured by NIKKO CHEMICALS Co., Ltd., Hinoact T-8000E and the like manufactured by Kawaken Fine Chemicals Co., Ltd., Organosiloxane Polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd., “W001: Cationic Surfactant” manufactured by Yusho Co., Ltd., nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan aliphatic acid ester, and anionic surfactants such as “W004, W005, and W017”, “EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, and EFKA polymer 450” manufactured by MORISHITA SANGYO Corporation, polymer dispersants such as “Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, and Disperse Aid 9100” manufactured by SAN NOPCO Ltd., “Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, and P-123” manufactured by ADEKA CORPORATION, and “Ionet (product name) S-20” manufactured by Sanyo Chemical Industries, Ltd.

These pigment dispersants may be used alone or in combination of two or more kinds thereof. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymer dispersant. Further, the pigment dispersant may be used in combination with an alkali-soluble resin, together with a terminal-modified polymer having a moiety anchored to the pigment surface, a graft polymer, or a block polymer. Examples of the alkali-soluble resin include a (meth)acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, and an acidic cellulose derivative having a carboxylic acid in a side chain, and a (meth)acrylic acid copolymer is particularly preferable. In addition, the N-position-substituted maleimide monomers copolymer described in JP1998-300922A (JP-H10-300922A), the ether dimer copolymers described in JP2004-300204A, and the alkali-soluble resins containing a polymerizable group described in JP1995-319161A (JP-H07-319161A) are also preferable.

The total content of the pigment dispersant in the coloring composition is preferably 1 part by mass to 80 parts by mass, more preferably 5 parts by mass to 70 parts by mass, and still more preferably 10 parts by mass to 60 parts by mass, with respect to 100 parts by mass of the pigment.

Specifically, in the case where a polymer dispersant is used, the amount of the polymer dispersant used is preferably 5 parts by mass to 100 parts by mass, and more preferably 10 parts by mass to 80 parts by mass, with respect to 100 parts by mass of the pigment.

Moreover, in the case where a pigment derivative is used in combination with other components, the amount of the pigment derivative used is preferably 1 part by mass to 30 parts by mass, more preferably 3 parts by mass to 20 parts by mass, and particularly preferably 5 parts by mass to 15 parts by mass, with respect to 100 parts by mass of the pigment.

In the coloring composition, from the viewpoint of curing sensitivity and color density, the total content of the coloring agent components and the pigment dispersant is preferably 50% by mass to 90% by mass, more preferably 55% by mass to 85% by mass, and still more preferably 60% by mass to 80% by mass, with respect to the total solid contents constituting the coloring composition.

<Photopolymerization Initiator (D)>

From the viewpoint of further improving sensitivity, it is preferable that the coloring composition of the present invention contains a photopolymerization initiator.

The photopolymerization initiator is not particularly limited as long as the photopolymerization initiator has a function of initiating polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, photopolymerization initiators sensitive to light rays in a range from ultraviolet region to visible light are preferable. In addition, the photopolymerization initiator may be either an activator which interacts with a photo-excited sensitizer in any way and generates active radicals or an initiator which initiates cationic polymerization according to the type of monomer.

Furthermore, it is preferable that the photopolymerization initiator contains at least one kind of compound having at least a molar absorption coefficient of about 50 in a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, a derivative having a triazine skeleton, and a derivative having an oxadiazole skeleton), acyl phosphine compounds such as acyl phosphine oxide, oxime compounds such as hexaaryl biimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenone.

Furthermore, from the viewpoint of exposure sensitivity, the compound is preferably a compound selected from a group consisting of a trihalomethyl triazine compound, a benzyl dimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acyl phosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triallylimidazole dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound and a derivative thereof, a cyclopentadiene-benzene-iron complex and a salt thereof, a halomethyl oxadiazole compound, and a 3-aryl-substituted coumarin compound.

The compound is more preferably a trihalomethyl triazine compound, an α-aminoketone compound, an acyl phosphine compound, a phosphine oxide compound, an oxime compound, a triallylimidazole dimer, a triarylimidazole compound, a benzoimidazole compound, an onium compound, a benzophenone compound, or an acetophenone compound, and particularly preferably at least one kind of compound selected from a group consisting of a trihalomethyl triazine compound, an α-aminoketone compound, an oxime compound, a triallylimidazole compound, a benzophenone compound, a triarylimidazole compound, and a benzoimidazole compound. Further, the triarylimidazole compound may be a mixture thereof with benzoimidazole.

Specifically, the trihalomethyltriazine compound is exemplified as follows. Incidentally, Ph is a phenyl group.

As the triarylimidazole compound and the benzoimidazole compound, the following compounds are exemplified.

As the trihalomethyltriazine compound, a commercially available product can also be used, and for example, TAZ-107 (manufactured by Midori Kagaku Co., Ltd.) can also be used.

Particularly, in the case where the coloring composition of the present invention is used for the manufacture of a color filter for a solid-state imaging element, a fine pattern needs to be formed in a sharp shape. Accordingly, it is important that the composition has curability and is developed without residues in an unexposed area. From this viewpoint, an oxime compound is particularly preferable as a polymerization initiator. In particular, in the case where a fine pattern is formed in the solid-state imaging element, stepper exposure is used for exposure for curing. However, the exposure machine used at this time is damaged by halogen in some cases, so it is necessary to reduce the amount of a polymerization initiator added. In consideration of this point, in order to form a fine pattern as in a solid-state imaging element, it is most preferable to use an oxime compound as the photopolymerization initiator (D).

Examples of the halogenated hydrocarbon compound having a triazine skeleton include the compounds described in Wakabayashi, et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), the compounds described in UK1388492B, the compounds described in JP1978-133428A (JP-553-133428A), the compounds described in GE3337024B, the compound described in F. C. Schaefer, et al., J. Org. Chem., 29, 1527 (1964), the compounds described in JP1987-58241A (JP-562-58241A), the compounds described in JP1993-281728A (JP-H05-281728A), the compounds described in JP1993-34920A (JP-H05-34920A), and the compounds described in U.S. Pat. No. 4,212,976A.

Examples of the compounds described in U.S. Pat. No. 4,212,976A include compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-chlorophenyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(1-naphthyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(2-naphthyl)-1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5-(2-naphthyl)-1,3,4-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-chlorostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-methoxystyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(1-naphthyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-n-butoxystyryl)-1,3,4-oxadiazole, and 2-tribromomethyl-5-styryl-1,3,4-oxadiazole).

Examples of photopolymerization initiators other than the above include acridine derivatives (for example, 9-phenylacridine and 1,7-bis(9,9′-acridinyl)heptane), N-phenylglycine, polyhalogen compounds (for example, carbon tetrabromide, phenyl tribromomethyl sulfone, and phenyl trichloromethyl ketone), coumarins (for example, 3-(2-benzofuranoyl)-7-diethylaminocoumarin, 3-(2-benzofuroyl)-7-(1-pyrrolidinyl)coumarin, 3-benzoyl-7-diethylaminocoumarin, 3-(2-methoxybenzoyl)-7-diethylaminocoumarin, 3-(4-dimethylaminobenzoyl)-7-diethylaminocoumarin, 3,3′-carbonyl bis(5,7-di-n-propoxycoumarin), 3,3′-carbonyl bis(7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3-(2-furoyl)-7-diethylaminocoumarin, 3-(4-diethylaminocinnamoyl)-7-diethylaminocoumarin, 7-methoxy-3-(3-pyridylcarbonyl)coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, and coumarin compounds described in JP1993-19475A (JP-H05-19475A), JP1995-271028A (JP-H07-271028A), JP2002-363206A, JP2002-363207A, JP2002-363208A, JP2002-363209A, and the like), acyl phosphine oxides (for example, bis(2,4,6-trimethylbenzoyl)-phenyl phosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphenyl phosphine oxide, and Lucirin TPO), metallocenes (for example, bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, and η5-cyclopentadienyl-η6-cumenyl-iron(1+)-hexafluorophosphate (1−)), the compounds described in JP1978-133428A (JP-S53-133428A), JP1982-1819B (JP-S57-1819B), JP1982-6096B (JP-S57-6096B), and U.S. Pat. No. 3,615,455A, and the like.

Examples of the ketone compounds include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenone tetracarboxylic acid or a tetramethyl ester thereof, 4,4′-bis(dialkylamino)benzophenones for example, 4,4′-bis(dimethylamino)benzophenone, 4,4′-bis(dicyclohexylamino)benzophenone, 4,4′-bis(diethylamino)benzophenone, 4,4′-bis(dihydroxyethylamino)benzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 4,4′-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-tert-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chloro-thioxanthone, 2,4-diethylthioxanthone, fluorenone, 2-benzyl-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, a 2-hydroxy-2-methyl-[4-(1-methylvinyl)phenyl]propanol oligomer, benzoin, benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin phenyl ether, and benzyl dimethyl ketal), acridone, chloroacridone, N-methylacridone, N-butylacridone, and N-butyl-chloroacridone.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acyl phosphine compound can also be suitably used. More specifically, for example, the aminoacetophenone-based initiator described in JP1998-291969A (JP-H10-291969A), and the acyl phosphine oxide-based initiator described in JP4225898B can also be used.

As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (product names, all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-OXE379 (product names, all manufactured by BASF) which are commercially available products can be used. In addition, as the aminoacetophenone-based initiator, the compound described in JP2009-191179A, of which an absorption wavelength matches with a light source of a long wavelength of 365 nm, 405 nm, or the like can be used. Moreover, as the acyl phosphine-based initiator, IRGACURE-819 or DAROCUR-TPO (product name, both manufactured by BASF) which are commercially available products can be used.

Examples of the photopolymerization initiator more preferably include oxime compounds. As specific examples of the oxime compounds, the compound described in JP2001-233842A, the compound described in JP2000-80068A, or the compound described in JP2006-342166A can be used.

Examples of the oxime compound such as an oxime derivative, which is suitably used as the photopolymerization initiator in the present invention, include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.

Examples of the oxime compound include the compounds described in J. C. S. Perkin II (1979), pp. 1653-1660, J. C. S. Perkin II (1979), pp. 156-162, Journal of Photopolymer Science and Technology (1995), pp. 202-232, and JP2000-66385A; and the compounds described respectively in JP2000-80068A, JP2004-534797A, and JP2006-342166A.

As the commercially available product, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also suitably used. Further, TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can also be suitably used.

Furthermore, as oxime compounds other than the above, the compound described in JP2009-519904A in which oxime is linked to an N-position of carbazole, the compound described in U.S. Pat. No. 7,626,957B in which a hetero-substituent is introduced into a benzophenone site, the compounds described in JP2010-15025A and US2009/292039A in which a nitro group is introduced into a dye site, the ketoxime compound described in WO2009/131189A, the compound described in U.S. Pat. No. 7,556,910B which contains a triazine skeleton and an oxime skeleton in the same molecule, the compound described in JP2009-221114A, which has maximum absorption at 405 nm and has excellent sensitivity to a light source of a g-ray, and the like may be used.

Preferably, the cyclic oxime compounds described in JP2007-231000A and JP2007-322744A can also be suitably used. Among the cyclic oxime compounds, the cyclic oxime compounds ring-fused to a carbazole dye, which are described in JP2010-32985A and JP2010-185072A, are preferable from the viewpoint of high sensitivity since these compounds have high light absorptivity.

Furthermore, the compound described in JP2009-242469A, which is an oxime compound having an unsaturated bond in a specific moiety, can also be suitably used since this compound makes it possible to improve sensitivity by reproducing active radicals from polymerization-inactive radicals.

The most preferred examples of the oxime compounds include the oxime compound having a specific substituent described in JP2007-269779A and the oxime compound having a thioaryl group described in JP2009-191061A.

Specifically, the oxime compound which is a photopolymerization initiator is preferably a compound represented by the following General Formula (OX-1). Incidentally, the compound may be an oxime compound in which an N—O bond of oxime forms an (E) isomer, an oxime compound in which the N—O bond forms a (Z) isomer, or a mixture in which the N—O bond forms a mixture of an (E) isomer and a (Z) isomer.

In General Formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.

In General Formula (OX-1), the monovalent substituent represented by R is preferably a monovalent non-metal atomic group.

Examples of the monovalent non-metal atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Further, these groups may have one or more substituents. Moreover, the aforementioned substituents may further be substituted with other substituents.

Examples of the substituents include a halogen atom, an aryloxy group, an alkoxycarbonyl or aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.

The alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, an octadecyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a 1-ethylpentyl group, a cyclopentyl group, a cyclohexyl group, a trifluoromethyl group, a 2-ethylhexyl group, a phenacyl group, a 1-naphthoylmethyl group, a 2-naphthoylmethyl group, a 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, a 4-dimethylaminophenacyl group, a 4-cyanophenacyl group, a 4-methylphenacyl group, a 2-methylphenacyl group, a 3-fluorophenacyl group, a 3-trifluoromethylphenacyl group, and a 3-nitrophenacyl group.

The aryl group is preferably an aryl group having 6 to 30 carbon atoms, and specific examples thereof include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 9-phenanthryl group, a 1-pyrenyl group, a 5-naphthacenyl group, a 1-indenyl group, a 2-azulenyl group, a 9-fluorenyl group, a terphenyl group, an octaphenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a xylyl group, an o-cumenyl group, an m-cumenyl group, a p-cumenyl group, a mesityl group, a pentalenyl group, a binaphthalenyl group, a ternaphthalenyl group, a quaternaphthalenyl group, a heptalenyl group, a biphenylenyl group, an indacenyl group, a fluoranthenyl group, an acenaphthylenyl group, an aceanthrylenyl group, a phenalenyl group, a fluorenyl group, an anthryl group, a bianthracenyl group, a teranthracenyl group, a quateranthracenyl group, an anthraquinolyl group, a phenanthryl group, a triphenylenyl group, a pyrenyl group, a chrysenyl group, a naphthacenyl group, a pleiadenyl group, a picenyl group, a perylenyl group, a pentaphenyl group, a pentacenyl group, a tetraphenylenyl group, a hexaphenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an ovalenyl group.

The acyl group is preferably an acyl group having 2 to 20 carbon atoms, and specific examples thereof include an acetyl group, a propanoyl group, a butanoyl group, a trifluoroacetyl group, a pentanoyl group, a benzoyl group, a 1-naphthoyl group, a 2-naphthoyl group, a 4-methylsulfanylbenzoyl group, a 4-phenylsulfanylbenzoyl group, a 4-dimethylaminobenzoyl group, a 4-diethylaminobenzoyl group, a 2-chlorobenzoyl group, a 2-methylbenzoyl group, a 2-methoxybenzoyl group, a 2-butoxybenzoyl group, a 3-chlorobenzoyl group, a 3-trifluoromethylbenzoyl group, a 3-cyanobenzoyl group, a 3-nitrobenzoyl group, a 4-fluorobenzoyl group, a 4-cyanobenzoyl group, and a 4-methoxybenzoyl group.

The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, and specific examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a hexyloxycarbonyl group, an octyloxycarbonyl group, a decyloxycarbonyl group, an octadecyloxycarbonyl group, and a trifluoromethyloxycarbonyl group.

Specific examples of the aryloxycarbonyl group include a phenoxycarbonyl group, a 1-naphthyloxycarbonyl group, a 2-naphthyloxycarbonyl group, a 4-methylsulfanylphenyloxycarbonyl group, a 4-phenylsulfanylphenyloxycarbonyl group, a 4-dimethylaminophenyloxycarbonyl group, a 4-diethylaminophenyloxycarbonyl group, a 2-chlorophenyloxycarbonyl group, a 2-methylphenyloxycarbonyl group, a 2-methoxyphenyloxycarbonyl group, a 2-butoxyphenyloxycarbonyl group, a 3-chlorophenyloxycarbonyl group, a 3-trifluoromethylphenyloxycarbonyl group, a 3-cyanophenyloxycarbonyl group, a 3-nitrophenyloxycarbonyl group, a 4-fluorophenyloxycarbonyl group, a 4-cyanophenyloxycarbonyl group, and a 4-methoxyphenyloxycarbonyl group.

As the heterocyclic group, an aromatic or aliphatic heterocycle having a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom is preferable.

Specific examples of the heterocyclic group include a thienyl group, a benzo[b]thienyl group, a naphtho[2,3-b]thienyl group, a thianthrenyl group, a furyl group, a pyranyl group, an isobenzofuranyl group, a chromenyl group, a xanthenyl group, a phenoxathiinyl group, a 2H-pyrrolyl group, a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, an indolizinyl group, an isoindolyl group, a 3H-indolyl group, an indolyl group, a 1H-indazolyl group, a purinyl group, a 4H-quinolizinyl group, an isoquinolyl group, a quinolyl group, a phthalazinyl group, a naphthyridinyl group, a quinoxalinyl group, a quinazolinyl group, a cinnolinyl group, a pteridinyl group, a 4aH-carbazolyl group, a carbazolyl group, a 3-carbolinyl group, a phenanthrydinyl group, an acridinyl group, a perimidinyl group, a phenanthrolinyl group, a phenazinyl group, a phenarsazinyl group, an isothiazolyl group, a phenothiazinyl group, an isoxazolyl group, a furazanyl group, a phenoxazinyl group, an isochromanyl group, a chromanyl group, a pyrrolidinyl group, a pyrrolinyl group, an imidazolidinyl group, an imidazolinyl group, a pyrazolidinyl group, a pyrazolinyl group, a piperidyl group, a piperazinyl group, an indolinyl group, an isoindolinyl group, a quinuclidinyl group, a morpholinyl group, and a thioxantolyl group.

Specific examples of the alkylthiocarbonyl group include a methylthiocarbonyl group, a propylthiocarbonyl group, a butylthiocarbonyl group, a hexylthiocarbonyl group, an octylthiocarbonyl group, a decylthiocarbonyl group, an octadecylthiocarbonyl group, and a trifluoromethylthiocarbonyl group.

Specific examples of the arylthiocarbonyl group include a 1-naphthylthiocarbonyl group, a 2-naphthylthiocarbonyl group, a 4-methylsulfanylphenylthiocarbonyl group, a 4-phenylsulfanylphenylthiocarbonyl group, a 4-dimethylaminophenylthiocarbonyl group, a 4-diethylaminophenylthiocarbonyl group, a 2-chlorophenylthiocarbonyl group, a 2-methylphenylthiocarbonyl group, a 2-methoxyphenylthiocarbonyl group, a 2-butoxyphenylthiocarbonyl group, a 3-chlorophenylthiocarbonyl group, a 3-trifluoromethylphenylthiocarbonyl group, a 3-cyanophenylthiocarbonyl group, a 3-nitrophenylthiocarbonyl group, a 4-fluorophenylthiocarbonyl group, a 4-cyanophenylthiocarbonyl group, and a 4-methoxyphenylthiocarbonyl group.

In General Formula (OX-1), the monovalent substituent represented by B represents an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents, and examples of the substituents include the aforementioned substituents. In addition, the aforementioned substituents may be further substituted with other substituents.

Among these, the following structures are particularly preferable.

In the following structures, Y, X, and n have the same definitions as Y, X, and n, respectively, in General Formula (OX-2) which will be described later, and the preferred examples thereof are also the same.

In Formula (OX-1), examples of the divalent organic group represented by A include an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, and an alkynylene group, and these groups may have one or more substituents. Examples of the substituents include the aforementioned substituents. Further, the aforementioned substituents may further substituted with other substituents.

Among these, as A in Formula (OX-1), from the viewpoints of improving sensitivity and inhibiting coloring caused by elapse of time during heating, an unsubstituted alkylene group, an alkylene group substituted with an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, and a dodecyl group), an alkylene group substituted with an alkenyl group (for example, a vinyl group and an allyl group), and an alkylene group substituted with an aryl group (for example, a phenyl group, a p-tolyl group, a xylyl group, a cumenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a styryl group) are preferable.

In Formula (OX-1), the aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms, and may have a substituent. Examples of the substituent include the same ones as the substituents introduced into the substituted aryl groups, which are exemplified above as specific examples of the aryl group which may have a substituent.

Among these, from the viewpoints of improving sensitivity and inhibiting coloration caused by elapse of time during heating, a substituted or unsubstituted phenyl group is preferable.

In Formula (OX-1), a structure “SAr” formed of Ar and S adjacent thereto in Formula (OX-1) is preferably the following structure from the viewpoints of sensitivity. Incidentally, Me represents a methyl group, and Et represents an ethyl group.

The oxime compound is preferably a compound represented by the following General Formula (OX-2).

In General Formula (OX-2), R and X each independently represent a monovalent substituent, A and Y each independently represent a divalent organic group, Ar represents an aryl group, and n represents an integer of 0 to 5. R, A, and Ar in General Formula (OX-2) have the same definitions as R, A, and Ar, respectively, in General Formula (OX-1), and the preferred examples thereof are also the same.

Examples of the monovalent substituent represented by X in General Formula (OX-2) include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, an amino group, a heterocyclic group, and a halogen atom. These groups may have one or more substituents, and examples of the substituents include the aforementioned substituents. Moreover, the aforementioned substituents may be further substituted with other substituents.

Among these, from the viewpoints of improving solvent solubility and absorption efficiency in a long-wavelength region, X in General Formula (OX-2) is preferably an alkyl group.

Furthermore, n in Formula (2) represents an integer of 0 to 5 and preferably represents an integer of 0 to 2.

Examples of the divalent organic group represented by Y in General Formula (OX-2) include the following structures. In the following groups, “*” represents a position where Y binds to a carbon atom adjacent thereto in Formula (OX-2).

Among these, from the viewpoints of improving sensitivity, the following structures are preferable.

Moreover, the oxime compound is preferably a compound represented by the following General Formula (OX-3) or (OX-4).

In General Formula (OX-3) or (OX-4), R and X each independently represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, and n represents an integer of 0 to 5.

R, X, A, Ar, and n in General Formula (OX-3) or (OX-4) have the same definitions as R, X, A, Ar, and n, respectively, in General Formula (OX-2), and the preferred examples thereof are also the same.

Specific examples (C-4) to (C-13) of the oxime compound which are preferably used are shown below, but the present invention is not limited thereto.

The oxime compound has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, and preferably has an absorption wavelength in a wavelength region of 360 nm to 480 nm, and an oxime compound showing a high absorbance at 365 nm and 455 nm is particularly preferable.

From the viewpoint of sensitivity, the molar absorption coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, and more preferably 2,000 to 300,000, and particularly preferably 5,000 to 200,000.

The molar absorption coefficient of the compound can be measured using a known method, but specifically, it is preferable to measure the molar absorption coefficient by means of, for example, an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) by using an ethyl acetate solvent at a concentration of 0.01 g/L.

The photopolymerization initiator used in the present invention may be used in combination of two or more kinds thereof, as desired.

In the case where the coloring composition of the present invention contains the photopolymerization initiator (D), the content of the photopolymerization initiator (D) is preferably 0.1% by mass to 50% by mass, more preferably 0.5% by mass to 30% by mass, and still more preferably 1% by mass to 20% by mass, with respect to the total solid contents of the coloring composition. Within this range, improved sensitivity and pattern formability are obtained.

<Alkali-Soluble Resin (F)>

It is preferable that the coloring composition of the present invention further contains an alkali-soluble resin. Incidentally, the alkali-soluble resin as mentioned herein does not include the components contained as the pigment dispersant in the coloring composition of the present invention.

The alkali-soluble resin can be appropriately selected from alkali-soluble resins which are linear organic high molecular-weight polymers and have at least one group enhancing alkali-solubility in a molecule (preferably, a molecule having an acrylic copolymer or a styrene-based copolymer as a main chain). From the viewpoint of heat resistance, a polyhydroxystyrene-based resin, a polysiloxane-based resin, an acrylic resin, an acrylamide-based resin, and an acryl/acrylamide copolymer resin are preferable. Further, from the viewpoint of controlling developability, an acrylic resin, an acrylamide-based resin, and an acryl/acrylamide copolymer resin are preferable.

Examples of the group promoting alkali-solubility (hereinafter also referred to as an “acid group”) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxyl group, and the like. The group promoting alkali-solubility is preferably a group which is soluble in an organic solvent and can be developed by an aqueous weak alkaline solution, and particularly preferred examples thereof include a (meth)acrylic acid. These acid groups may be used alone or in combination of two or more kinds thereof.

Examples of the monomer which can give the acid group after polymerization include monomers having a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate, monomers having an epoxy group, such as glycidyl (meth)acrylate, and monomers having an isocyanate group, such as 2-isocyanatoethyl (meth)acrylate. The monomers for introducing these acid groups may be used alone or in combination of two or more kinds thereof. In order to introduce the acid group into the alkali-soluble resin, for example, the monomer having the acid group and/or the monomer which can give the acid group after polymerization (hereinafter referred to as a “monomer for introducing an acid group” in some cases) may be polymerized as a monomer component.

Incidentally, in the case where a monomer which can give the acid group after polymerization is used as a monomer component to introduce the acid group, a treatment for giving the acid group, which will be described later, needs to be performed after polymerization.

For production of the alkali-soluble resin, for example, a method using known radical polymerization can be applied. Various polymerization conditions for producing the alkali-soluble resin by radical polymerization, such as a temperature, a pressure, the type and amount of a radical initiator, and the type of a solvent, can be easily set by those skilled in the art, and the conditions can also be determined experimentally.

As the linear organic high-molecular weight polymer used as the alkali-soluble resin, polymers having a carboxylic acid in a side chain are preferable, and examples thereof include a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, an alkali-soluble phenol resin or the like such as a novolac resin, an acidic cellulose derivative having a carboxylic acid in a side chain, and a polymer obtained by adding an acid anhydride to a polymer having a hydroxyl group. In particular, a copolymer of a (meth)acrylic acid and another monomer copolymerizable with the (meth)acrylic acid is suitable as the alkali-soluble resin. Examples of another monomer copolymerizable with a (meth)acrylic acid include alkyl (meth)acrylate, aryl (meth)acrylate, and a vinyl compound. Examples of the alkyl (meth)acrylate and aryl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, tolyl (meth)acrylate, naphthyl (meth)acrylate, and cyclohexyl (meth)acrylate. Examples of the vinyl compound include styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, a polystyrene macromonomer, and a polymethyl methacrylate macromonomer. Examples of the N-position-substituted maleimide monomer disclosed in JP1998-300922A (JP-H10-300922A) include N-phenylmaleimide and N-cyclohexylmaleimide. Incidentally, other monomers copolymerizable with a (meth)acrylic acid may be used alone or in combination of two or more kinds thereof.

It is also preferable that the coloring composition contains, as the alkali-soluble resin, a polymer (a) obtained by polymerizing monomer components including a compound represented by the following General Formula (ED) (hereinafter also referred to as an “ether dimer” in some cases) as an essential component.

In General Formula (ED), R¹ and R² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms, which may have a substituent.

Thus, the coloring composition of the present invention can form a cured coating film which has extremely excellent heat resistance as well as transparency. In General Formula (ED) which represents the ether dimer, the hydrocarbon group having 1 to 25 carbon atom, represented by R¹ and R², which may have a substituent, is not particularly limited, and examples thereof include linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl, and 2-ethylhexyl; aryl groups such as phenyl; alicyclic groups such as cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, and 2-methyl-2-adamantyl; alkyl groups substituted with alkoxy such as 1-methoxyethyl and 1-ethoxyethyl; and alkyl groups substituted with an aryl group such as benzyl. Among these, from the viewpoints of heat resistance, substituents of primary or secondary carbon, which are not easily eliminated by an acid or heat, such as methyl, ethyl, cyclohexyl, and benzyl, are preferable.

Specific examples of the ether dimer include dimethyl-2,2′-[oxybis(methylene)]bis-2-propenoate, diethyl-2,2′-[oxybis(methylene)]bis-2-propenoate, di(n-propyl)-2,2′-[oxybis(methylene)]bis-2-propenoate, di(isopropyl)-2,2′-[oxybis(methylene)]bis-2-propenoate, di(n-butyl)-2,2′-[oxybis(methylene)]bis-2-propenoate, di(isobutyl)-2,2′-[oxybis(methylene)]bis-2-propenoate, di(tert-butyl)-2,2′-[oxybis(methylene)]bis-2-propenoate, di(tert-amyl)-2,2′-[oxybis(methylene)]bis-2-propenoate, di(stearyl)-2,2′-[oxybis(methylene)]bis-2-propenoate, di(lauryl)-2,2′-[oxybis(methylene)]bis-2-propenoate, di(2-ethylhexyl)-2,2′-[oxybis(methylene)]bis-2-propenoate, di(1-methoxyethyl)-2,2′-[oxybis(methylene)]bis-2-propenoate, di(1-ethoxyethyl)-2,2′-[oxybis(methylene)]bis-2-propenoate, dibenzyl-2,2′-[oxybis(methylene)]bis-2-propenoate, diphenyl-2,2′-[oxybis(methylene)]bis-2-propenoate, dicyclohexyl-2,2′-[oxybis(methylene)]bis-2-propenoate, di(tert-butylcyclohexyl)-2,2′-[oxybis(methylene)]bis-2-propenoate, di(dicyclopentadienyl)-2,2′-[oxybis(methylene)]bis-2-propenoate, di(tricyclodecanyl)-2,2′-[oxybis(methylene)]bis-2-propenoate, di(isobornyl)-2,2′-[oxybis(methylene)]bis-2-propenoate, diadamantyl-2,2′-[oxybis(methylene)]bis-2-propenoate, and di(2-methyl-2-adamantyl)-2,2′-[oxybis(methylene)]bis-2-propenoate. Among these, dimethyl-2,2′-[oxybis(methylene)]bis-2-propenoate, diethyl-2,2′-[oxybis(methylene)]bis-2-propenoate, dicyclohexyl-2,2′-[oxybis(methylene)]bis-2-propenoate, and dibenzyl-2,2′-[oxybis(methylene)]bis-2-propenoate are particularly preferable. These ether dimers may be used alone or in combination of two or more kinds thereof. The structure derived from the compound represented by General Formula (ED) may be copolymerized with other monomers.

Moreover, in order to improve the crosslinking efficiency of the coloring composition in the present invention, an alkali-soluble resin having a polymerizable group may be used. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resins and the like containing an allyl group, a (meth)acryl group, an allyloxyalkyl group, and the like on a side chain thereof are useful.

Examples of the polymer containing the above polymerizable group include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (a polyurethane acrylic oligomer containing COOH, manufactured by Diamond Shamrock Co., Ltd.), Biscoat R-264 and KS Resist 106 (all manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.), Cyclomer P series and Placcel CF200 series (all manufactured by DAICEL Corporation), and Ebecryl 3800 (manufactured by DAICEL-UCB Co., Ltd.). As the alkali-soluble resin containing a polymerizable group, a polymerizable double bond-containing acrylic resin modified with urethane, which is a resin obtained by a reaction of an isocyanate group and an OH group in advance to leave an unreacted isocyanate group and performing a reaction between a compound having a (meth)acryloyl group and an acrylic resin having a carboxyl group, an unsaturated bond-containing acrylic resin which is obtained by a reaction between an acrylic resin having a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in a molecule, a polymerizable double bond-containing acrylic resin which is obtained by a reaction between an acid pendant type epoxy acrylate resin, an acrylic resin having an OH group, and a dibasic acid anhydride having a polymerizable double bond, a resin obtained by a reaction between an acrylic resin having an OH group and a compound having isocyanate and a polymerizable group, a resin which is obtained by treating a resin, which has an ester group having an elimination group such as a halogen atom or a sulfonate group in an α-position or a β-position described in JP2002-229207A and JP2003-335814A on a side chain, with a base, and the like are preferable.

As the alkali-soluble resin, particularly, a benzyl (meth)acrylate/(meth)acrylic acid copolymer or a multicomponent copolymer including benzyl (meth)acrylate/(meth)acrylic acid/other monomers is suitable. Examples thereof also include a benzyl (meth)acrylate/methacrylic acid/2-hydroxyethyl methacrylate copolymer obtained by copolymerizing 2-hydroxyethyl methacrylate, a 2-hydroxypropyl (meth)acrylate/a polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer described in JP1995-140654A (JP-H07-140654A), a 2-hydroxy-3-phenoxypropyl acrylate/a polymethyl methacrylate macromonomer/benzyl methacrylate/methacrylic acid copolymer, a 2-hydroxyethyl methacrylate/a polystyrene macromonomer/methyl methacrylate/methacrylic acid copolymer, and a 2-hydroxyethyl methacrylate/a polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, and particularly preferably a copolymer of benzyl methacrylate/methacrylic acid.

With respect to the alkali-soluble resin, reference can be made to the descriptions in paragraphs “0558” to “0571” of JP2012-208494A (“0685” to “0700” of the corresponding to US2012/0235099A), the contents of which are incorporated herein.

Furthermore, it is preferable to use the copolymers (B) described in paragraph Nos. “0029” to “0063” of JP2012-32767A and the alkali-soluble resins used in Examples of the document; the binder resins described in paragraph Nos. “0088” to “0098” of JP2012-208474A and the binder resins used in Examples of the document, the binder resins described in paragraph Nos. “0022” to “0032” of JP2012-137531A and the binder resins in Examples of the document, the binder resins described in paragraph Nos. “0132” to “0143” of JP2013-024934A and the binder resins used in Examples of the document, the binder resins described in paragraph Nos. “0092” to “0098” of JP2011-242752A and used in Examples of the document, or the binder resins described in paragraph Nos. “0030” to 0072″ of JP2012-032770A, the contents of which are incorporated herein. More Specifically, the following resins are preferable.

The acid value of the alkali-soluble resin is preferably 30 mgKOH/g to 200 mgKOH/g, more preferably 50 mgKOH/g to 150 mgKOH/g, and most preferably 70 mgKOH/g to 120 mgKOH/g.

Furthermore, the weight-average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, and most preferably 7,000 to 20,000. The molecular weight of the compound used in the present invention can be measured by a method using gel permeation chromatography (GPC) and is defined as a value in terms of polystyrene by GPC measurement. For example, the molecular weight can be determined with HLC-8220 GPC (manufactured by Tosoh Corporation) by using TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6.0 mm ID×15.0 cm) as a column and a 10 mmol/L solution of lithium bromide in NMP (N-methylpyrrolidone) as an eluant.

In the case where the coloring composition contains an alkali-soluble resin, the content of the alkali-soluble resin in the coloring composition is preferably 1% by mass to 15% by mass, more preferably 2% by mass to 12% by mass, and particularly preferably 3% by mass to 10% by mass, with respect to the total solid contents of the coloring composition.

The coloring composition of the present invention may include one kind or two or more kinds of alkali-soluble resin. In the case where the coloring composition includes two or more kinds of the alkali-soluble resin, the total amount thereof is preferably within the range.

<Other Components>

The coloring composition of the present invention may further contain other components such as an organic solvent and a crosslinking agent, in addition to the respective components described above, within a range which does not diminish the effects of the present invention.

<<Organic Solvent>>

The coloring composition of the present invention may contain an organic solvent.

Basically, the organic solvent is not particularly limited as long as the solvent satisfies the solubility of the respective components or the coatability of the coloring composition. In particular, it is preferable to select the organic solvent in consideration of the solubility, coatability, and safety of an ultraviolet absorber, the alkali-soluble resin, the dispersant, or the like. In addition, when the coloring composition in the present invention is prepared, the composition preferably includes at least two kinds of organic solvents.

Suitable examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate (for example, methyl oxyacetate, ethyl oxyacetate, and butyl oxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate)), alkyl 3-oxypropionate esters (for example, methyl 3-oxypropionate and ethyl 3-oxypropionate (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-ethoxypropionate)), alkyl 2-oxypropionate esters (for example, methyl 2-oxypropionate, ethyl 2-oxypropionate, or propyl 2-oxypropionate (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, or ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methyl propionate and ethyl 2-oxy-2-methyl propionate (for example, methyl 2-methoxy-2-methyl propionate and ethyl 2-ethoxy-2-methyl propionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, and ethyl 2-oxobutanoate; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; and aromatic hydrocarbons such as toluene and xylene.

From the viewpoint of the solubility of an ultraviolet absorber and the alkali-soluble resin, and improvement of the shape of the coated surface, it is also preferable to mix two or more kinds of these organic solvents. In this case, a mixed solution consisting of two or more kinds selected from the aforementioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethylcarbitol acetate, butylcarbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate is particularly preferable.

From the viewpoint of coatability, the content of the organic solvent in the coloring composition is set such that the concentration of the total solid contents of the composition becomes preferably 5% by mass to 80% by mass, more preferably 5% by mass to 60% by mass, and particularly preferably 10% by mass to 50% by mass.

<<Crosslinking Agent>>

It is also possible to improve the hardness of the cured film obtained by curing the coloring composition by using a crosslinking agent complementarily in the coloring composition of the present invention.

The crosslinking agent is not particularly limited as long as it makes it possible to cure a film by a crosslinking reaction, and examples thereof include (a) an epoxy resin, (b) a melamine compound, a guanamine compound, a glycoluril compound, or a urea compound substituted with at least one substituent selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group, and (c) a phenol compound, a naphthol compound, or a hydroxyanthracene compound, which is substituted with at least one substituent selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Among these, a polyfunctional epoxy resin is preferable.

With regard to the details of specific examples and the like of the crosslinking agent, reference can be made to the description of paragraphs “0134” to “0147” of JP2004-295116A.

In the case where the coloring composition of the present invention contains a crosslinking agent, the blending amount of the crosslinking agent is not particularly limited, but is preferably 2% by mass to 30% by mass, and more preferably 3% by mass to 20% by mass, with respect to the total solid contents of the composition.

The coloring composition of the present invention may include one kind or two or more kinds of crosslinking agent. In the case where the coloring composition includes two or more kinds of the crosslinking agent, the total amount thereof is preferably within the range.

<<Polymerization Inhibitor>>

It is preferable to add a small amount of a polymerization inhibitor to the coloring composition of the present invention in order to suppress the occurrence of unnecessary thermal polymerization of the polymerizable compound during production or storage of the coloring composition.

Examples of the polymerization inhibitor which can be used in the present invention include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis(3-methyl-6-tert-butylphenol), 2,2′-methylenebis(4-methyl-6-tert-butylphenol), and cerium (III) N-nitrosophenyl hydroxylamine salt.

In the case where the coloring composition of the present invention contains a polymerization inhibitor, the amount of the polymerization inhibitor added is preferably about 0.01% by mass to about 5% by mass, with respect to the total mass of the composition.

The composition of the present invention may include one kind or two or more kinds of polymerization inhibitor. In the case where the composition includes two or more kinds of the polymerization inhibitor, the total amount thereof is preferably within the range.

<<Surfactant>>

From the viewpoint of further improving coatability, various surfactants may be added to the coloring composition of the present invention. As the surfactants, it is possible to use various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant.

Particularly, if the coloring composition of the present invention contains a fluorine-based surfactant, liquid characteristics (particularly, fluidity) are further improved when the composition is prepared as a coating liquid, whereby evenness of the coating thickness or liquid saving properties can be further improved.

That is, in the case where a coating liquid obtained by applying the coloring composition containing a fluorine-based surfactant is used to form a film, the surface tension between a surface to be coated and the coating liquid is reduced to improve wettability with respect to the surface to be coated, and enhance coatability with respect to the surface to be coated. Therefore, even in the case where a thin film of about several μm is formed of a small amount of liquid, the coloring composition containing a fluorine-based surfactant is effective in that a film with a uniform thickness which exhibits a small extent of thickness unevenness can be more suitably formed.

The fluorine content in the fluorine-based surfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. The fluorine-based surfactant in which the fluorine content is within this range is effective in terms of the evenness of the thickness of the coating film or liquid saving properties, and the solubility of the surfactant in the coloring composition is also good.

Examples of the fluorine-based surfactant include Megaface F171, Megaface F172, Megaface F173, Megaface F176, Megaface F177, Megaface F141, Megaface F142, Megaface F143, Megaface F144, Megaface R30, Megaface F437, Megaface F475, Megaface F479, Megaface F482, Megaface F554, Megaface F780, and Megaface F781 (all manufactured by DIC Corporation), Fluorad FC430, FC431, and FC171 (all manufactured by Sumitomo 3M), and Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon 393, and Surflon KH-40 (all manufactured by ASAHI GLASS Co., Ltd.).

Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and ethoxylate and propoxylate thereof (for example, glycerol propoxylate and glycerin ethoxylate), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters (Pluronic L10, L31, L61, L62, 10R5, 17R2, and 25R2, and Tetronic 304, 701, 704, 901, 904, and 150R1 manufactured by BASF), and Solseperse 20000 (manufactured by The Lubrizol Corporation).

Specific examples of the cationic surfactant include phthalocyanine derivatives (product name: EFKA-745 manufactured by MORISHITA SANGYO Corporation), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid-based (co)polymer Polyflow No. 75, No. 90, and No. 95 (manufactured by KYOEISHA CHEMICAL CO., LTD.), and W001 (manufactured by Yusho Co., Ltd.).

Specific examples of the anionic surfactant include W004, W005, and W017 (manufactured by Yusho Co., Ltd.).

Examples of the silicone-based surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Toray Silicone DC11PA”, “Toray Silicone SH21PA”, “Toray Silicone SH28PA”, “Toray Silicone SH29PA”, “Toray Silicone SH30PA”, and “Toray Silicone SH8400”, manufactured by Dow Corning Toray, “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-4460”, and “TSF-4452”, manufactured by Momentive Performance Materials Inc., “KP341”, “KF6001”, and “KF6002”, manufactured by Shin-Etsu Silicones, and “BYK307”, “BYK323”, and “BYK330”, manufactured by BYK-Chemie.

The surfactants may be used alone or in combination of two or more kinds thereof.

In the case where the coloring composition of the present invention contains a surfactant, the amount of the surfactant added is preferably 0.001% by mass to 2.0% by mass and more preferably 0.005% by mass to 1.0% by mass, with respect to the total mass of the coloring composition.

The composition of the present invention may include one kind or two or more kinds of surfactant. In the case where the composition includes two or more kinds of the surfactant, the total amount thereof is preferably within the range.

<<Other Additives>>

If desired, various additives such as a filler, an adhesion promoting agent, an antioxidant, an ultraviolet absorber, and an anti-aggregation agent may be blended into the coloring composition. Examples of these additives include those described in paragraphs “0155” and “0156” of JP2004-295116A.

The coloring composition of the present invention can contain the sensitizer or the light stabilizer described in paragraph “0078” of JP2004-295116A, and the thermal polymerization inhibitor described in paragraph “0081” of JP2004-295116A.

<<Organic Carboxylic Acid and Organic Carboxylic Anhydride>>

The coloring composition of the present invention may contain an organic carboxylic acid having a molecular weight of 1000 or less, and/or an organic carboxylic anhydride.

Specific examples of the organic carboxylic acid compound include an aliphatic carboxylic acid and an aromatic carboxylic acid. Examples of the aliphatic carboxylic acid include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, glycolic acid, acrylic acid, and methacrylic acid, dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, and fumaric acid, tricarboxylic acids such as tricarballylic acid, and aconitic acid, and the like. Examples of the aromatic carboxylic acid include carboxylic acids in which a carboxyl group is directly bonded to a phenyl group such as a benzoic acid and a phthalic acid, and carboxylic acids in which a phenyl group is bonded to a carboxyl group via a carbon bond. Among these, carboxylic acids having a molecular weight of 600 or less, particularly those having a molecular weight of 50 to 500, and specifically, maleic acid, malonic acid, succinic acid, and itaconic acid are preferable.

Examples of the organic carboxylic anhydride include aliphatic carboxylic anhydride and aromatic carboxylic anhydride. Specific examples thereof include aliphatic carboxylic anhydrides such as acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2-cyclohexenedicarboxylic anhydride, n-octadecylsuccinic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride. Examples of the aromatic carboxylic anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride. Among these, those having a molecular weight of 600 or less, particularly having a molecular weight of 50 to 500, specifically, for example, maleic anhydride, succinic anhydride, citraconic anhydride, and itaconic anhydride are particularly preferable.

In the case where the coloring composition of the present invention contains an organic carboxylic acid or an organic carboxylic anhydride, the amount of these organic carboxylic acids and/or the organic carboxylic anhydrides added is generally in a range of 0.01% by mass to 10% by mass, preferably 0.03% by mass to 5% by mass, and more preferably 0.05% by mass to 3% by mass in the total solid contents.

By adding these organic carboxylic acids and/or the organic carboxylic anhydrides having a molecular weight of 1000 or less, it is possible to further reduce the amount of the residual undissolved substance of the coloring composition while maintaining high pattern adhesiveness.

<Method for Producing Coloring Composition>

The coloring composition of the present invention is prepared by mixing the aforementioned components.

Incidentally, when the coloring composition is prepared, the respective components constituting the coloring composition may be mixed together at the same time or mixed together sequentially after being dissolved and dispersed in a solvent. Further, the order of adding the components and the operation conditions during the mixing are not particularly restricted. For example, all the components may be dissolved and dispersed in a solvent at the same time to prepare the composition. Alternatively, if desired, the respective components may be appropriately prepared as two or more solutions and dispersions and mixed at the time of use (at the time of coating) to prepare the composition.

The coloring composition prepared as above can be provided for use after being filtered using a filter having a pore diameter of preferably 0.01 μm to 3.0 μm, and more preferably about 0.05 μm to 0.5 μm, or the like.

Since the coloring composition of the present invention can form a cured film having excellent heat resistance and color characteristics, the coloring composition of the present invention is suitably used for forming a colored pattern (colored layer) of a color filter. Further, the coloring composition of the present invention can be suitably used for forming a colored pattern of a color filter or the like used in a solid-state imaging element (for example, a CCD and a CMOS) or an image display device such as a liquid crystal display (LCD). Further, the composition can also be suitably used in an application of the manufacture of a print ink, an ink jet ink, a coating material, or the like. Among these, the composition can be suitably used in an application of the manufacture of a color filter for a solid-state imaging element such as a CCD and a CMOS.

<Cured Film, Pattern Forming Method, Color Filter, and Method for Producing Color Filter>

Next, the cured film, the pattern forming method, and the color filter in the present invention will be described in detail by an explanation of production methods thereof.

A first embodiment of the pattern forming method of the present invention may include a step of applying the coloring composition of the present invention onto a support to form a coloring composition layer, a step of patternwise exposing the coloring composition layer, and a step of removing an unexposed area by development to form a colored pattern.

Furthermore, a second embodiment of the pattern forming method of the present invention may include a step of applying the coloring composition of the present invention onto a support to form a coloring composition layer, curing the coloring composition layer to form a colored layer, a step of forming a photoresist layer on the colored layer, a step of patterning the photoresist layer by exposure and development to obtain a resist pattern, and a step of dry-etching the colored layer using the resist pattern as an etching mask to form a colored pattern.

That is, in the present invention, a pattern can be formed by photolithography or a dry etching method.

The pattern forming method of the present invention can be suitably applied for forming a colored pattern (pixel) included in a color filter.

The support for forming a pattern by the pattern forming method of the present invention is not particularly limited as long as it is a support that can be applied for pattern formation, in addition to a planar material such as a substrate.

The respective steps in the pattern forming method of the present invention will be described in detail below with reference to the method for producing a color filter for a solid-state imaging element, but the present invention is not limited to this method.

The method for producing a color filter of the present invention involves applying the pattern forming method of the present invention, and includes a step of forming a colored pattern on a support using the pattern forming method of the present invention. That is, the pattern forming method of the present invention is applied to the method for producing a color filter of the present invention.

A first embodiment of the method for producing a color filter of the present invention includes a step of applying the coloring composition of the present invention onto a support to form a coloring composition layer, a step of patternwise exposing the coloring composition layer, and a step of removing an unexposed area by development to form a colored pattern. Further, it may include a step of baking the coloring composition layer (a pre-baking step), and a step of baking the developed colored pattern (a post-baking step). Hereafter, these steps are collectively referred to as a pattern forming step in some cases.

In addition, a second embodiment of the method for producing a color filter of the present invention may include a step of applying the coloring composition of the present invention onto a support to form a coloring composition layer and curing the coloring composition layer to form a colored layer, a step of forming a photoresist layer on the colored layer, a step of patterning the photoresist layer by exposure and development to obtain a resist pattern, and a step of dry-etching the colored layer using the resist pattern as an etching mask to form a colored pattern.

The color filter of the present invention can be suitably obtained by the production method.

Hereafter, the color filter for a solid-state imaging element may be simply referred to as a “color filter” in some cases.

The respective steps in the pattern forming method of the present invention will be described in detail below with reference to the method for producing a color filter of the present invention.

The method for producing a color filter of the present invention involves applying the pattern forming method of the present invention, and includes a step of forming a colored pattern on a substrate using the pattern forming method of the present invention.

<Step of Forming Coloring Composition Layer>

In the step of forming a coloring composition layer, the coloring composition of the present invention is applied onto a support to form a coloring composition layer.

As the support which can be used in the present step, for example, a substrate for a solid-state imaging element, which is formed by providing an imaging element (light-receiving element) such as a charge coupled device (CCD) or a complementary metal-oxide semiconductor (CMOS) onto a substrate (for example, a silicon substrate) can be used.

The colored pattern in the present invention may be formed on the surface (front surface) on which an imaging element is formed or on the surface (back surface) where an imaging element is not formed, of a substrate for a solid-state imaging element.

A light shielding film may be disposed between the colored patterns in a solid-state imaging element or on the back surface of the substrate for a solid-state imaging element.

In addition, if desired, an undercoat layer may be disposed onto the support in order to improve adhesiveness between the support and the upper layer, prevent diffusion of substances, or planarize the substrate surface.

As the method for applying the coloring composition of the present invention onto the support, various coating methods such as slit coating, ink jet coating, spin coating, cast coating, roll coating, and screen printing can be applied.

Drying (pre-baking) of the coloring composition layer applied onto the support can be carried out in a hot plate, an oven, or the like at a temperature of 50° C. to 140° C. for 10 seconds to 300 seconds.

<<Case of Forming Pattern by Photolithography Method>>

<<<Exposing Step>>>

In the exposing step, the coloring composition layer formed in the coloring composition layer forming step is patternwise exposed through a mask having a predetermined mask pattern by using, for example, an exposure device such as a stepper. Thus, a cured film is obtained.

As radiation (light) usable in exposure, particularly, ultraviolet rays such as a g-ray and an i-ray are preferably used (particularly, an i-ray is preferably used). The irradiation dose (exposure dose) is preferably 30 mJ/cm² to 1500 mJ/cm², more preferably 50 mJ/cm² to 1000 mJ/cm², and most preferably 80 mJ/cm² to 500 mJ/cm².

The film thickness of the cured film is preferably 1.0 μm or less, more preferably 0.1 μm to 0.9 μm, and still more preferably 0.2 μm to 0.8 μm.

It is preferable to set the film thickness to 1.0 μm or less since high resolution and high adhesiveness are obtained.

Moreover, in this step, a cured film having a small film thickness of 0.7 μm or less can be suitably formed. Further, if the obtained cured film is subjected to a development treatment in a pattern forming step which will be described later, it is possible to obtain a colored pattern which is a thin film and exhibits excellent developability and reduced surface roughness with an excellent pattern shape.

<<<Pattern Forming Step>>>

Thereafter, by performing an alkaline developing treatment, the coloring composition layer in an area not irradiated with light in the exposing step is eluted into an aqueous alkaline solution, and as a result, only a photocured area remains.

As a developing liquid, an organic alkaline developing liquid not damaging an imaging element, a circuit, or the like in an underlayer is preferable. The development temperature is usually 20° C. to 30° C., and the development time is 20 seconds to 90 seconds in the related art. In order to further remove residues, development is recently carried out for 120 seconds to 180 seconds in some cases. Further, in order to improve residue removal properties, a step of sufficiently shaking the developing liquid every 60 seconds and newly supplying a developing liquid is repeated plural times in some cases.

Examples of an alkaline agent used for the developing liquid include organic alkaline compounds such as aqueous ammonia, ethylamine, diethylamine, dimethyl ethanolamine, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide, benzyltrimethyl ammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo-[5,4,0]-7-undecene. An aqueous alkaline solution obtained by diluting these alkaline agents with pure water so as to yield a concentration of the alkaline agent of 0.001% by mass to 10% by mass, and preferably 0.01% by mass to 1% by mass is preferably used as the developing liquid.

Incidentally, inorganic alkali may be used for the developing liquid, and as the inorganic alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, sodium metasilicate, and the like are preferable.

Furthermore, in the case where a developing liquid formed of such an aqueous alkaline solution is used, the pattern is generally cleaned (rinsed) with pure water after development.

Next, it is preferable to carry out a heating treatment (post-baking) after drying. If a multi-colored pattern is formed, the above steps can be sequentially repeated for each color to produce a cured film. Thus, a color filter is obtained.

The post-baking is a heating treatment performed after development so as to complete curing, and in the post-baking, a thermal curing treatment is carried out usually at 100° C. to 240° C., and preferably at 200° C. to 240° C.

The post-baking treatment can be carried out on the coating film obtained after development in a continuous or batch manner, by using heating means such as a hot plate, a convection oven (a hot-air circulation type drier), and a high-frequency heater under the conditions described above.

<<Case of Forming Pattern By Dry Etching Method>>

With the colored layer, the dry etching can be carried out with an etching gas, using a patterned photoresist layer as a mask. Specifically, a positive-type or negative-type radiation-sensitive composition is applied onto the colored layer and dried to form a photoresist layer. In the formation of the photoresist layer, it is preferable to further carry out a pre-baking treatment. In particular, as a process for forming a photoresist, a configuration in which a post-exposure heating treatment (PEB) or a post-development heating treatment (post-baking treatment) is carried out is preferable.

As the photoresist, for example, a positive-type radiation-sensitive composition is used. As the positive-type radiation-sensitive composition, a positive-type resist composition suitable for a positive-type photoresist, which responds to radiation, for example, an ultraviolet ray (a g-ray, an h-ray, or an i-ray), a far ultraviolet ray including an excimer laser and the like, an electron beam, an ion beam, or an X-ray, can be used. Among the radiations, a g-ray, an h-ray, or an i-ray is preferable, among which the i-ray is more preferable.

Specifically, as the positive-type radiation-sensitive composition, a composition containing a quinonediazide compound and an alkali-soluble resin is preferable. The positive-type radiation-sensitive composition containing a quinonediazide compound and an alkali-soluble resin utilizes a quinonediazide group being decomposed to generate a carboxyl group by light irradiation at a wavelength of 500 nm or less, and as a result, the quinonediazide compound is shifted from an alkali-insoluble state to an alkali-soluble state. Since this positive-type photoresist is remarkably excellent in the resolving power, it is used for the manufacture of an integrated circuit, for example, IC and LSI. Examples of the quinonediazide compound include a naphthoquinonediazide compound. Examples of commercially available products thereof include “FHi622BC” (manufactured by FUJIFILM Electronics Materials Co., Ltd.).

The thickness of the photoresist layer is preferably 0.1 μm to 3 μm, more preferably 0.2 μm to 2.5 μm, and still more preferably 0.3 μm to 2 μm. Incidentally, coating of the photoresist layer can be suitably carried out using the coating method described with respect to the above-described colored layer.

Next, a resist pattern (patterned photoresist layer) in which a resist through-hole group is disposed is formed by exposing and developing the photoresist layer. The formation of the resist pattern can be carried out by appropriately optimizing heretofore known techniques of photolithography without particular limitation. By providing the resist through-hole group in the photoresist layer by exposure and development, the resist pattern which is used as an etching mask in the subsequent etching is provided on the colored layer.

Exposure of the photoresist layer can be carried out by exposing a positive-type or negative-type radiation-sensitive composition to a g-ray, an h-ray, or an i-ray, and preferably to an i-ray through a predetermined mask pattern. After the exposure, a development treatment is carried out using a developing liquid to remove the photoresist corresponding to the region where a colored pattern is to be formed.

As the developing liquid, any developing liquid which does not affect a colored layer containing a coloring agent and dissolves the exposed area of a positive resist or the uncured area of a negative resist may be used, and for example, a combination of various organic solvents or an aqueous alkaline solution is used. As the aqueous alkaline solution, an aqueous alkaline solution prepared by dissolving an alkaline compound to yield a concentration of 0.001% by mass to 10% by mass, and preferably 0.01% by mass to 5% by mass is suitable. Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylemanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene. Incidentally, in the case where an aqueous alkaline solution is used as the developing liquid, a cleaning treatment with water is generally carried out after development.

Next, the colored layer is patterned by dry etching so as to form a through-hole group in the colored layer using the resist pattern as an etching mask. Thus, a colored pattern is formed. The through-hole group is provided checkerwise in the colored layer. Thus, a first colored pattern having the through-hole group provided in the colored layer has a plurality of first quadrangular colored pixels checkerwise.

It is preferable that the dry etching is carried out in a configuration as described below from the viewpoint of forming a pattern cross-section closer to that of a rectangle or of further reducing damage to a support.

A configuration is preferable, which includes a first-stage etching of etching up to an area (depth) where the support is not revealed by using a mixed gas of a fluorine-based gas and an oxygen gas (O₂), a second-stage etching of preferably etching up to the vicinity of an area (depth) where the support is revealed by using a mixed gas of a nitrogen gas (N₂) and an oxygen gas (O₂) after the first-stage etching, and an over-etching carried out after the support has been revealed. A specific manner of the dry etching as well as the first-stage etching, the second-stage etching, and the over-etching will be described below.

The dry etching is carried out by determining the etching conditions in advance in the following manner.

(1) An etching rate (nm/min) in the first-stage etching and an etching rate (nm/min) in the second-stage etching are calculated, respectively.

(2) A time for etching a predetermined thickness in the first-stage etching and a time for etching a predetermined thickness in the second-stage etching are calculated, respectively.

(3) The first-stage etching is carried out according to the etching time calculated in (2) above.

(4) The second-stage etching is carried out according to the etching time calculated in (2) above. Alternatively, an etching time is determined by endpoint detection, and the second-stage etching may be carried out according to the determined etching time.

(5) The over-etching time is calculated in response to the total time of (3) and (4) above, and the over-etching is carried out.

The mixed gas used in the first-stage etching step preferably contains a fluorine-based gas and an oxygen gas (O₂) from the viewpoint of processing an organic material of the film to be etched into a rectangle shape. The first-stage etching step may avoid damage to the support by adopting the configuration of etching up to an area where the support is not revealed. After the etching is carried out up to an area where the support is not revealed by the mixed gas of a fluorine-based gas and an oxygen gas in the first-stage etching step, etching treatment in the second-stage etching step and etching treatment in the over-etching step are preferably carried out by using the mixed gas of a nitrogen gas and an oxygen gas from the viewpoint of avoiding damage to the support.

It is important that a ratio between the etching amount in the first-stage etching step and the etching amount in the second-stage etching step is determined so as not to deteriorate the linearity by the etching treatment in the first-stage etching step. Incidentally, the ratio of the etching amount in the second-stage etching step in the total etching amount (the sum of the etching amount in the first-stage etching step and the etching amount in the second-stage etching step) is preferably in a range of more than 0% and 50% or less, and more preferably 10% to 20%. The etching amount means an amount determined by a difference between the remaining film thickness of the etched film and the film thickness of the film before the etching.

Furthermore, the etching preferably includes an over-etching treatment. The over-etching treatment is preferably carried out by determining an over-etching rate. The over-etching rate is preferably calculated from an etching treatment time which is carried out at first. Although the over-etching rate may be arbitrarily determined, it is preferably 30% or less, more preferably 5% to 25%, and particularly preferably 10% to 15%, of the etching processing time in the etching steps, from the viewpoint of etching resistance of the photoresist and preservation of the linearity of the etched pattern.

Next, the resist pattern (that is, the etching mask) remaining after the etching is removed. The removal of the resist pattern preferably includes a step of supplying a peeling solution or a solvent on the resist pattern to make the resist pattern be in a removable state, and a step of removing the resist pattern using cleaning water.

The step of supplying a peeling solution or a solvent on the resist pattern to make the resist pattern be in a removable state includes, for example, a step of paddle development by supplying a peeling solution or a solvent at least on the resist pattern and retaining for a predetermined time. The time for retaining the peeling solution or a solvent is not particularly limited, and is preferably several tens of seconds to several minutes.

Moreover, the step of removing the resist pattern using cleaning water includes, for example, a step of removing the resist pattern by spraying cleaning water from a spray-type or shower-type spray nozzles onto the resist pattern. As the cleaning water, pure water is preferably used. The spray nozzles include spray nozzles having a spray area which covers the entire support and mobile spray nozzles having a mobile area which covers the entire support. In the case where the spray nozzles are mobile spray nozzles, the resist pattern can be more effectively removed by moving the mobile spray nozzles twice or more from the center of support to the edge of the support to spray cleaning water in the step of removing the resist pattern.

The peeling solution generally contains an organic solvent and may further contain an inorganic solvent. Examples of the organic solvent include 1) a hydrocarbon-based compound, 2) a halogenated hydrocarbon-based compound, 3) an alcohol-based compound, 4) an ether- or acetal-based compound, 5) a ketone- or aldehyde-based compound, 6) an ester-based compound, 7) a polyhydric alcohol-based compound, 8) a carboxylic acid- or its acid anhydride-based compound, 9) a phenol-based compound, 10) a nitrogen-containing compound, 11) a sulfur-containing compound, and 12) a fluorine-containing compound. The peeling solution preferably contains a nitrogen-containing compound, and more preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound.

The acyclic nitrogen-containing compound is preferably an acyclic nitrogen-containing compound having a hydroxyl group. Specific examples thereof include monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-ethylethanolamine, N,N-dibutylethanolamine, N-butylethanolamine, monoethanolamine, diethanolamine, and triethanolamine, among which monoethanolamine, diethanolamine, and triethanolamine are preferable, and monoethanolamine (H₂NCH₂CH₂OH) is more preferable. Further, examples of the cyclic nitrogen-containing compound include isoquinoline, imidazole, N-ethylmorpholine, ε-caprolactam, quinoline, 1,3-dimethyl-2-imidazolidinone, α-picoline, β-picoline, γ-picoline, 2-pipecoline, 3-pipecoline, 4-pipecoline, piperazine, piperidine, pyrazine, pyridine, pyrrolidine, N-methyl-2-pyrrolidone, N-phenyl morpholine, 2,4-lutidine, and 2,6-lutidine, among which N-methyl-2-pyrrolidone and N-ethyl morpholine are preferable, and N-methyl-2-pyrrolidone (NMP) is more preferable.

The peeling solution preferably includes both the acyclic nitrogen-containing compound and the cyclic nitrogen-containing compound, more preferably contains at least one selected from monoethanolamine, diethanolamine, and triethanolamine as the acyclic nitrogen-containing compound, and at least one selected from N-methyl-2-pyrrolidone and N-ethyl morpholine as the cyclic nitrogen-containing compound, and still more preferably contains monoethanolamine and N-methyl-2-pyrrolidone.

In the removal with the peeling solution, it is sufficient that the resist pattern formed on the colored pattern is removed, and in a case where a deposit of an etching product is attached to the side wall of the colored pattern, it is not always necessary to completely remove the deposit. The deposit means an etching product attached and deposited to the side wall of colored layer.

For the peeling solution, it is preferable that the content of the acyclic nitrogen-containing compound is 9 parts by mass to 11 parts by mass with respect to 100 parts by mass of the peeling solution, and the content of the cyclic nitrogen-containing compound is 65 parts by mass to 70 parts by mass with respect to 100 parts by mass of the peeling solution. The peeling solution is preferably one prepared by diluting a mixture of the acyclic nitrogen-containing compound and the cyclic nitrogen-containing compound with pure water.

Incidentally, the method for producing a color filter of the present invention may have a step known as a method for producing a color filter for a solid-state imaging element, if desired, as a step other than the above steps. For example, the method may include a curing step of curing the formed colored pattern by heating and/or exposure, if desired, after the coloring composition layer forming step, the exposing step, and the pattern forming step are carried out.

Moreover, in order to efficiently clean off the contamination caused when a nozzle of an ejection portion or a piping portion of a coating device is clogged, or the coloring composition or a pigment adheres to or is precipitated or dried inside the coating machine, it is preferable to use the solvent relating to the coloring composition of the present invention as a cleaning liquid. In addition, the cleaning liquids described in JP1995-128867A (JP-H07-128867A), JP1995-146562A (JP-H07-146562A), JP1996-278637A (JP-H08-278637A), JP2000-273370A, JP2006-85140A, JP2006-291191A, JP2007-2101A, JP2007-2102A, JP2007-281523A, and the like can also be suitably used to remove and clean the coloring composition according to the present invention.

Among the above, alkylene glycol monoalkyl ether carboxylate and alkylene glycol monoalkyl ether are preferable.

These solvents may be used alone or as a mixture of two or more kinds thereof. In the case where two or more kinds thereof are mixed, it is preferable to mix a solvent having a hydroxyl group with a solvent not having a hydroxyl group. The mass ratio between the solvent having a hydroxyl group and the solvent not having a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, and still more preferably 20/80 to 80/20. A mixed solvent in which propylene glycol monomethyl ether acetate (PGMEA) is mixed with propylene glycol monomethyl ether (PGME) at a ratio of 60/40 is particularly preferable. Incidentally, in order to improve the permeability of the cleaning liquid with respect to the contaminant, it is preferable to add the aforementioned surfactants relating to the present composition to the cleaning liquid.

Since the color filter of the present invention uses the coloring composition of the present invention, exposure having an excellent exposure margin can be carried out, and the formed colored pattern (colored pixel) has an excellent pattern shape. Further, since the surface roughness of the pattern and the amount of residues in a developed area are inhibited, excellent color characteristics are exhibited.

The color filter of the present invention can be suitably used for a solid-state imaging element such as a CCD and a CMOS, and is particularly suitable for a CCD, a CMOS, and the like with a high resolution, having more than 1,000,000 pixels. The color filter for a solid-state imaging element of the present invention can be used as, for example, a color filter disposed between a light-receiving portion of each pixel constituting a CCD or a CMOS and a microlens for condensing light.

Incidentally, the film thickness of the colored pattern (colored pixel) in the color filter of the present invention is preferably 2.0 μm or less, more preferably 1.0 μm or less, and still more preferably 0.7 μm or less.

Moreover, the size (pattern width) of the colored pattern (colored pixel) is preferably 2.5 μm or less, more preferably 2.0 μm or less, and particularly preferably 1.7 μm or less.

[Solid-State Imaging Element]

The solid-state imaging element of the present invention includes the color filter of the present invention. The constitution of the solid-state imaging element of the present invention is not particularly limited as long as the solid-state imaging element is constituted to include the color filter in the present invention and functions as a solid-state imaging element. However, for example, the solid-state imaging element can be constituted as below.

That is, a constitution in which transfer electrodes consisting of a plurality of photodiodes and transfer electrodes formed of polysilicon or the like constituting a light-receiving area of a solid-state imaging element (a CCD imaging element, a CMOS imaging element, or the like) are arranged onto a support; a light shielding film which is opened only to the light-receiving portion of the photodiode and is formed of tungsten or the like is disposed onto the photodiodes and the transfer electrodes; a device protecting film which is formed for covering the entire surface of the light shielding film and the light receiving portion of the photodiodes and is formed of silicon nitride or the like is disposed onto the light shielding film; and the color filter for a solid-state imaging element of the present invention is disposed onto the device protecting film.

In addition, the solid-state imaging element may have a constitution in which light-condensing means (for example, a microlens or the like, which shall apply hereinafter) is disposed to a portion positioned on the device protecting portion and under the color filter (side close to the support), a constitution in which light-condensing means is disposed on the color filter, and the like.

[Image Display Device]

The color filter of the present invention can be used not only for a solid-state imaging element, but also for an image display device such as a liquid crystal display device and an organic EL display device. In particular, the color filter is suitable for the applications of a liquid crystal display device. The liquid crystal display device including the color filter of the present invention can display a high-quality image showing a good tone and having excellent display characteristics.

The definition of display devices or details of the respective display devices are described in, for example, “Electronic Display Device (Akio Sasaki, Kogyo Chosakai Publishing Co., Ltd., published in 1990)”, “Display Device (Toshiyuki Ibuki, Sangyo Publishing Co., Ltd., published in 1989), and the like. In addition, the liquid crystal display device is described in, for example, “Liquid Crystal Display Technology for Next Generation (edited by Tatsuo Uchida, Kogyo Chosakai Publishing Co., Ltd., published in 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and for example, the present invention can be applied to liquid crystal display devices employing various systems described in the “Liquid Crystal Display Technology for Next Generation”.

The color filter of the present invention may be used for a liquid crystal display device using a color TFT system. The liquid crystal display device using a color TFT system is described in, for example, “Color TFT Liquid Crystal Display (KYORITSU SHUPPAN Co., Ltd., published in 1996)”. Further, the present invention can be applied to a liquid crystal display device having an enlarged view angle, which uses an in-plane switching driving system such as IPS and a pixel division system such as MVA, or to STN, TN, VA, OCS, FFS, R-OCB, and the like.

In addition, the color filter in the present invention can be provided to a Color-filter On Array (COA) system which is a bright and high-definition system. In the liquid crystal display device of the COA system, the characteristics required for a color filter layer need to include characteristics required for an interlayer insulating film, that is, a low dielectric constant and resistance to a peeling solution in some cases, in addition to the generally required characteristics as described above. In the color filter of the present invention, a dye multimer having an excellent hue is used. Accordingly, the color purity, light-transmitting properties, and the like are good, and the tone of the colored pattern (pixel) is excellent. Consequently, a liquid crystal display device of a COA system which has a high resolution and is excellent in long-term durability can be provided. Incidentally, in order to satisfy the characteristics required for a low dielectric constant, a resin coat may be provided on the color filter layer.

These image display systems are described in, for example, p. 43 of “EL, PDP, and LCD Display Technologies and Recent Trend in Market (TORAY RESEARCH CENTER, Research Department, published in 2001)”, and the like.

The liquid crystal display device including the color filter in the present invention is constituted with various members such as an electrode substrate, a polarizing film, a phase difference film, a backlight, a spacer, and a view angle compensation film, in addition to the color filter of the present invention. The color filter of the present invention can be applied to a liquid crystal display device constituted with these known members. These members are described in, for example, “94 Market of Peripheral Materials And Chemicals of Liquid Crystal Display (Kentaro Shima, CMC Publishing Co., Ltd., published in 1994)” and “2003 Current Situation of Market Relating to Liquid Crystal and Prospects (Vol. 2) (Ryokichi Omote, Fuji Chimera Research Institute, Inc., published in 2003)”.

The backlight is described in SID Meeting Digest 1380 (2005) (A. Konno, et al.), December Issue of Monthly “Display”, 2005, pp. 18-24 (Yasuhiro Shima) and pp. 25-30 (Takaaki Yagi) of the literature, and the like.

If the color filter in the present invention is used in a liquid crystal display device, high contrast can be realized when the color filter is combined with a three-wavelength tube of a cold cathode tube known in the related art. Further, if a light source of LED in red, green, and blue (RGB-LED) is used as a backlight, a liquid crystal display device having high luminance, high color purity, and good color reproducibility can be provided.

EXAMPLES

Hereafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to Examples below as long as the object of the present invention is not impaired. Incidentally, “%” and “part(s)” are based on mass unless otherwise specified.

Synthesis Example 1 Synthesis of Dye (S-37)

Synthesis of a dye (S-37) was carried out in accordance with the following scheme.

45 g of β-carbomethoxypropionyl chloride synthesized by the method of EXAMPLE 6 in WO2011/022221A and 14 g of pentaerythritol were mixed in 100 ml of pyridine, and the obtained reaction mixture was purified by silica gel column chromatography to obtain 5 g of an intermediate (B-1).

A commerically available rhodamine B (10 g) was dissolved in 40 ml of chloroform, and 5 g of phosphoryl chloride was added thereto. The mixture was heated and refluxed for 2 hours, and 1.7 g of the intermediate (B-1) was added thereto. Further, the mixture was heated and refluxed for 2 hours, and then the solution was washed with water and dried over sodium sulfate. Then, the solvent was removed by distillation. The red residue was recrystallized from 100 ml of isopropanol to obtain 5 g of an intermediate (C-1). This intermediate (C-1) was added to 20 ml of a 1 N aqueous potassium hydroxide solution, and the mixture was stirred for 1 hour. Then, an aqueous solution of a lithium salt of bis(trifluoromethylsulfonyl)imide was added thereto, and the resulting precipitate was collected by filtration to obtain 4.5 g of (S-37).

Synthesis Example 2 Synthesis of Dye (S-40)

A dye (S-40) was synthesized in the same manner as in Synthesis Example 1, except that a lithium salt of tris(trifluoromethylsulfonyl)methide was used instead of a lithium salt of bis(trifluoromethylsulfonyl)imide in Synthesis Example 1.

Synthesis Example 3 Synthesis of Dye (S-26)

Synthesis of a dye (S-26) was carried out in accordance with the following scheme.

10 g of (A-1) was dissolved in 40 ml of chloroform, 5 g of phosphoryl chloride was added thereto, and the mixture was heated and refluxed for 2 hours. Then, 0.7 g of an intermediate (B-2) induced from dipentaerythritol by an ordinary method was added thereto. Further, the mixture was heated and refluxed for 2 hours, the solution was then washed with water, and dried over sodium sulfate, and then the solvent was removed by distillation. The red residue was recrystallized from 100 ml of isopropanol to obtain 5 g of an intermediate (C-1). This intermediate (C-1) was added to 20 ml of a 1 N aqueous potassium hydroxide solution, and the mixture was stirred for 1 hour. Then, an aqueous solution of a lithium salt of bis(trifluoromethylsulfonyl)imide was added thereto, and the resulting precipitate was collected by filtration to obtain 4.5 g of (S-26).

Synthesis Example 4 Synthesis of Dye (S-46)

A dye (S-46) was synthesized in the same manner as in Synthesis Example 3, except that rhodamine B was used instead of (A-1) and a lithium salt of tetrakis(pentafluorophenyl)borate was used instead of a lithium salt of bis(trifluoromethylsulfonyl)imide in Synthesis Example 3.

The other dyes were synthesized in the same manner as in Synthesis Examples 1 to 4.

Q, R, m, D, and n correspond to General Formula (I), respectively, below.

TABLE 3 Q R m D n Anion in D S-1 (1) COOH 1 a-pm-1 2 — S-2 (1) COOH 1 a-tp-1 2 (a-1) S-3 (1) COOH 1 a-xt-1 2 (a-1) S-4 (1) COOH 1 a-cn-1 2 (a-1) S-5 (7) COOH 1 a-pm-1 2 — S-6 (7) COOH 1 a-tp-1 2 (a-10) S-7 (7) COOH 1 a-xt-1 2 (a-10) S-8 (7) COOH 1 a-cn-1 2 (a-10) S-9 (10) COOH 1 a-pm-1 3 — S-10 (10) COOH 1 a-tp-1 3 (a-10) S-11 (10) COOH 1 a-xt-1 3 (a-10) S-12 (10) COOH 1 a-cn-1 3 (a-10) S-13 (13) COOH 1 a-tp-1 3 (a-10) S-14 (13) COOH 1 a-xt-1 3 (a-10) S-15 (13) COOH 1 a-cn-1 3 (a-10) S-16 (14) COOH 1 a-pm-1 4 — S-17 (14) COOH 1 a-tp-1 4 (a-10) S-18 (14) COOH 1 a-xt-1 4 (a-10) S-19 (14) COOH 1 a-cn-1 4 (a-10) S-20 (15) SO₃H 1 a-pm-1 4 — S-21 (15) SO₃H 1 a-tp-1 4 (a-10) S-22 (15) SO₃H 1 a-xt-1 4 (a-10) S-23 (15) SO₃H 1 a-cn-1 4 (a-10) S-24 (16) COOH 1 a-pm-1 5 — S-25 (16) COOH 1 a-tp-1 5 (a-10) S-26 (16) COOH 1 a-xt-1 5 (a-10) S-27 (16) COOH 1 a-cn-1 5 (a-10) S-28 (15) COOH 2 a-pm-1 2 — S-29 (15) COOH 2 a-tp-1 2 (a-10) S-30 (15) COOH 2 a-xt-1 2 (a-10) S-31 (15) COOH 2 a-cn-1 2 (a-10) S-32 (16) COOH 2 a-pm-1 4 — S-33 (16) COOH 2 a-tp-1 4 (a-21) S-34 (16) COOH 2 a-xt-1 4 (a-21) S-35 (16) COOH 2 a-cn-1 4 (a-21) S-36 (10) COOH 1 a-xt-6 3 (a-10) S-37 (10) COOH 1 a-xt-7 3 (a-10) S-38 (10) COOH 1 a-xt-10 3 (a-10) S-39 (10) COOH 1 a-xt-6 3 (a-15) S-40 (10) COOH 1 a-xt-7 3 (a-15) S-41 (10) COOH 1 a-xt-10 3 (a-15) S-42 (16) COOH 2 a-xt-6 4 (a-14) S-43 (16) COOH 2 a-xt-7 4 (a-14) S-44 (16) COOH 2 a-xt-10 4 (a-14) S-45 (16) COOH 1 a-xt-6 5 (a-21) S-46 (16) COOH 1 a-xt-7 5 (a-21) S-47 (16) COOH 1 a-xt-10 5 (a-21) S-48 (16) COOH 3 a-xt-7 3 (a-11) S-49 (16) CH₂COOH 1 a-xt-7 5 (a-11) S-50 (16) PO₃H₂ 1 a-xt-7 5 (a-11)

The molecular weight of (S-51) was 3622 and the molecular weight of (S-52) was 4146.

Hereinbelow, the dye residue D is shown. * is a portion binding to Q.

Synthesis Example 5 Synthesis of Dyes (48) and (52) Synthesis of Dye (D4′)

Synthesis of the dye (D4′) was carried out in accordance with the following scheme.

150 g of pentafluorobenzenesulfonyl chloride was dissolved in 3000 mL of tetrahydrofuran (THF), and 68.4 g of 28% aqueous ammonia was added thereto at −10° C. under a nitrogen gas flow. The mixture was stirred at 0° C. for 1 hour, and then the reaction solution was filtered to remove ammonium chloride. The solution was concentrated under reduced pressure to remove THF, and then 1000 mL of water was added thereto at 0° C. to perform recrystallization. The resultant was further filtered to obtain 117.1 g of a compound (A-1).

985 mL of methanol and 49.0 g of 2-mercaptoethanol were added to 150 g of the obtained compound (A-1), and 64.5 g of triethylamine was added thereto at room temperature under a nitrogen air flow. The mixture was stirred at room temperature for 1 hour, and then the reaction solution was concentrated under reduced pressure to remove methanol. 900 mL of ethyl acetate, 800 mL of a saturated saline solution, and 100 mL of a saturated aqueous sodium bicarbonate solution were added to the concentrated compound to perform a liquid separation operation, and further, the organic layer was cleaned with water three times. The obtained organic layer was dehydrated over magnesium sulfate, and then the organic layer was concentrated under reduced pressure to remove ethyl acetate, thereby obtaining 169.7 g of a compound (A-2).

95 mL of dimethylacetamide (DMAc), 24.8 g of 2-isocyanatoethyl acrylate (AOI), and 0.190 g of dibutylhydroxytoluene (BHT) were added to obtain 48.8 g of a compound (A-2), and then 0.100 g of NEOSTANN U-600 was added thereto at room temperature under a nitrogen air flow. The mixture was stirred at 85° C. for 1 hour, and then cooled to room temperature, and 500 mL of ethyl acetate and 500 mL of a saturated saline solution were added thereto to perform a liquid separation operation. Further, the organic layer was cleaned with water three times. The obtained organic layer was dehydrated over magnesium sulfate, and then the organic layer was concentrated under reduced pressure to remove ethyl acetate. 170 mL of chloroform was added to the concentrated compound at 0° C. to perform recrystallization. The resultant was further filtered to obtain 59.7 g of a compound (A-3).

500 mL of methylene chloride and 34.0 g of triethylamine were added to 50.0 g of the obtained compound (A-3), and 108.0 g of acid chloride (A-4) was added thereto at room temperature under a nitrogen air flow. The mixture was stirred at room temperature for 2 hours, and then 200 mL of chloroform, 500 mL of water, and 200 mL of a saturated saline solution were added thereto to perform a liquid separation operation. The obtained organic layer was dehydrated over magnesium sulfate, concentrated under reduced pressure to remove ethyl acetate, and then purified by silica gel column chromatography (eluent solvent chloroform:ethyl acetate=10:1→5:5). A solution of the desired product was concentrated under reduced pressure, and 400 mL of acetonitrile was added to the obtained solid. The mixture was stirred for 1 hour and then filtered to obtain 108.0 g of a dye (D4′).

<<Synthesis of Dye (48)>>

Synthesis of a dye (48) was carried out in accordance with the following scheme.

1.0 g of dipentaerythritol hexakis(3-mercaptopropionate) [DPMP; manufactured by SAKAI CHEMICAL INDUSTRY. CO., LTD.], and 0.16 g of the compound (B-1) having an adsorption site as well as a carbon-carbon double bond were dissolved in 3.9 g of N-ethyl-2-pyrrolidone (NEP), and the solution was heated at 70° C. under a nitrogen air flow. 7.66 mg of 2,2′-azobis(2,4-dimethylvaleronitrile) [V-65, manufactured by Wako Pure Chemical Industries, Ltd.] was added thereto and the mixture was heated for 3 hours. Further, 7.66 mg of V-65 was added thereto and the mixture was allowed to undergo a reaction at 70° C. for 3 hours under a nitrogen air flow. The mixture was cooled to room temperature to obtain an NEP solution including 30% by mass of the compound (B-2).

Next, 9.6 g of NEP, 0.57 g of triethylamine, and 4.40 g of the dye (D4′) were added to 4.0 g of the NEP solution including 30% by mass of the compound (B-2), and the mixture was reacted at room temperature for 1 day. Thereafter, the reaction solution was added dropwise to 300 mL of a hexane:ethyl acetate (1:5) solution to perform a reprecipitation, and the mixture was further filtered to obtain 4.6 g of an oligomer (B-3).

Furthermore, 24 mL of DMAc, 0.22 g of 2-isocyanatoethyl methacrylate (MOI), and 0.10 g of BHT were added to 3.0 g of the oligomer (B-3), and the mixture was allowed to undergo a reaction at room temperature for 3 hours. Thereafter, the reaction solution was added dropwise to 300 mL of a hexane:ethyl acetate (1:5) solution to perform a reprecipitation, and the mixture was further filtered to obtain 1.9 g of a dye (48).

<<Synthesis of Dye (52)>>

Synthesis of a dye (52) was carried out in accordance with the following scheme.

1.0 g of dipentaerythritolhexakis(3-mercaptopropionate) [DPMP; manufactured by SAKAI CHEMICAL INDUSTRY. CO., LTD.], and 0.33 g of the compound (A-1) having an adsorption site as well as a carbon-carbon double bond were dissolved in 4.3 g of NEP, and the solution was heated at 70° C. under a nitrogen air flow. 7.66 mg of 2,2′-azobis(2,4-dimethylvaleronitrile) [V-65, manufactured by Wako Pure Chemical Industries, Ltd.] was added thereto and the mixture was heated for 3 hours. Further, 7.66 mg of V-65 was added thereto and the mixture was allowed to undergo a reaction at 70° C. for 3 hours under a nitrogen air flow. The mixture was cooled to room temperature to obtain an NEP solution including 30% by mass of a compound (C-1).

Next, 9.6 g of NEP, 0.51 g of triethylamine, and 5.13 g of the dye (D4′) were added to 4.0 g of the NEP solution including 30% by mass of the compound (C-1), and the mixture was stirred for 1 day. Thereafter, the reaction solution was added dropwise to 300 mL of a hexane:ethyl acetate (1:5) solution to perform a reprecipitation, and the mixture was further filtered to obtain 4.8 g of a dye (52).

The other dyes were synthesized in the same manner as in Synthesis Example 4.

Q, R, m, D, and n correspond to General Formula (I), respectively, below.

TABLE 4 R Number Type of Number Type of of R⁴'s, Compound Number acid of R²'s polymerizable R⁵'s, or No. D n Q of R¹'s group or R³'s group R⁶'s 1 D¹ 3 Q¹ 0 R² 2 R⁴ 1 2 D¹ 3 Q¹ 0 R² 1 R⁴ 2 3 D¹ 3 Q¹ 0 R³ 2 R⁴ 1 4 D¹ 3 Q¹ 0 R³ 1 R⁴ 2 5 D¹ 3 Q¹ 0 R³ 1 R⁵ 2 6 D¹ 3 Q¹ 0 R³ 1 R⁶ 2 7 D¹ 4 Q¹ 1 R² 1 — 0 8 D¹ 4 Q¹ 0 R² 2 — 0 9 D¹ 4 Q¹ 1 R³ 1 — 0 10 D¹ 4 Q¹ 0 R³ 2 — 0 11 D¹ 4 Q¹ 0 R² 1 R⁴ 1 12 D¹ 4 Q¹ 0 R³ 1 R⁴ 1 13 D¹ 4 Q¹ 0 R³ 1 R⁵ 1 14 D¹ 4 Q¹ 0 R³ 1 R⁶ 1 15 D² 3 Q¹ 0 R² 2 R⁴ 1 16 D² 3 Q¹ 0 R² 1 R⁴ 2 17 D² 3 Q¹ 0 R³ 2 R⁴ 1 18 D² 3 Q¹ 0 R³ 1 R⁴ 2 19 D² 3 Q¹ 0 R³ 1 R⁵ 2 20 D² 3 Q¹ 0 R³ 1 R⁶ 2 21 D² 4 Q¹ 1 R² 1 — 0 22 D² 4 Q¹ 0 R² 2 — 0 23 D² 4 Q¹ 1 R³ 1 — 0 24 D² 4 Q¹ 0 R³ 2 — 0 25 D² 4 Q¹ 0 R² 1 R⁴ 1 26 D² 4 Q¹ 0 R³ 1 R⁴ 1 27 D² 4 Q¹ 0 R³ 1 R⁵ 1 28 D² 4 Q¹ 0 R³ 1 R⁶ 1 29 D³ 3 Q¹ 0 R² 2 R⁴ 1 30 D³ 3 Q¹ 0 R² 1 R⁴ 2 31 D³ 3 Q¹ 0 R³ 2 R⁴ 1 32 D³ 3 Q¹ 0 R³ 1 R⁴ 2 33 D³ 3 Q¹ 0 R³ 1 R⁵ 2 34 D³ 3 Q¹ 0 R³ 1 R⁶ 2 35 D³ 4 Q¹ 1 R² 1 — 0 39 D³ 4 Q¹ 0 R² 1 R⁴ 1 40 D³ 4 Q¹ 0 R³ 1 R⁴ 1 41 D³ 4 Q¹ 0 R³ 1 R⁵ 1 42 D³ 4 Q¹ 0 R³ 1 R⁶ 1 43 D⁴ 3 Q¹ 0 R² 2 R⁴ 1 44 D⁴ 3 Q¹ 0 R² 1 R⁴ 2 45 D⁴ 3 Q¹ 0 R³ 2 R⁴ 1 46 D⁴ 3 Q¹ 0 R³ 1 R⁴ 2 47 D⁴ 3 Q¹ 0 R³ 1 R⁵ 2 48 D⁴ 3 Q¹ 0 R³ 1 R⁶ 2 49 D⁴ 4 Q¹ 1 R² 1 — 0 50 D⁴ 4 Q¹ 0 R² 2 — 0 51 D⁴ 4 Q¹ 1 R³ 1 — 0 52 D⁴ 4 Q¹ 0 R³ 2 — 0 53 D⁴ 4 Q¹ 0 R² 1 R⁴ 1 54 D⁴ 4 Q¹ 0 R³ 1 R⁴ 1 55 D⁴ 4 Q¹ 0 R³ 1 R⁵ 1

TABLE 5 R Number Type of Number Type of of R⁴'s, Compound Number acid of R²'s polymerizable R⁵'s, or No. D n Q of R¹'s group or R³'s group R⁶'s 56 D⁴ 4 Q¹ 0 R³ 1 R⁶ 1 57 D⁵ 3 Q² 0 R² 2 R⁴ 1 58 D⁵ 3 Q² 0 R² 1 R⁴ 2 59 D⁵ 3 Q² 0 R³ 2 R⁴ 1 60 D⁵ 3 Q² 0 R³ 1 R⁴ 2 61 D⁵ 3 Q² 0 R³ 1 R⁵ 2 62 D⁵ 3 Q² 0 R³ 1 R⁶ 2 63 D⁵ 4 Q² 1 R² 1 — 0 64 D⁵ 4 Q² 0 R² 2 — 0 65 D⁵ 4 Q² 1 R³ 1 — 0 66 D⁵ 4 Q² 0 R³ 2 — 0 67 D⁵ 4 Q² 0 R² 1 R⁴ 1 68 D⁵ 4 Q² 0 R³ 1 R⁴ 1 69 D⁵ 4 Q² 0 R³ 1 R⁵ 1 70 D⁵ 4 Q² 0 R³ 1 R⁶ 1 71 D⁶ 1 Q³ 0 R² 1 R⁴ 1 72 D⁶ 1 Q³ 0 R³ 1 R⁴ 1 73 D⁶ 1 Q³ 0 R³ 1 R⁵ 1 74 D⁶ 1 Q³ 0 R³ 1 R⁶ 1 75 D⁶ 2 Q³ 0 R³ 1 — 0 76 D⁷ 3 Q¹ 0 R² 2 R⁴ 0 77 D⁷ 3 Q¹ 0 R² 1 R⁴ 0 78 D⁷ 3 Q¹ 0 R³ 2 R⁴ 0 79 D⁷ 3 Q¹ 0 R³ 1 R⁴ 0 80 D⁷ 3 Q¹ 0 R³ 1 R⁵ 0 81 D⁷ 3 Q¹ 0 R³ 1 R⁶ 0 82 D⁷ 4 Q¹ 1 R² 1 — 0 83 D⁷ 4 Q¹ 0 R² 2 — 0 84 D⁷ 4 Q¹ 1 R³ 1 — 0 85 D⁷ 4 Q¹ 0 R³ 2 — 0 86 D⁷ 4 Q¹ 0 R² 1 R⁴ 0 87 D⁷ 4 Q¹ 0 R³ 1 R⁴ 0 88 D⁷ 4 Q¹ 0 R³ 1 R⁵ 0 89 D⁷ 4 Q¹ 0 R³ 1 R⁶ 0 90 D⁸ 3 Q² 0 R² 2 R⁴ 0 91 D⁸ 3 Q² 0 R² 1 R⁴ 0 92 D⁸ 3 Q² 0 R³ 2 R⁴ 0 93 D⁸ 3 Q² 0 R³ 1 R⁴ 0 94 D⁸ 3 Q² 0 R³ 1 R⁵ 0 95 D⁸ 3 Q² 0 R³ 1 R⁶ 0 96 D⁸ 4 Q² 1 R² 1 — 0 97 D⁸ 4 Q² 0 R² 2 — 0 98 D⁸ 4 Q² 1 R³ 1 — 0 99 D⁸ 4 Q² 0 R³ 2 — 0 100 D⁸ 4 Q² 0 R² 1 R⁴ 0 101 D⁸ 4 Q² 0 R³ 1 R⁴ 0 102 D⁸ 4 Q² 0 R³ 1 R⁵ 0 103 D⁸ 4 Q² 0 R³ 1 R⁶ 0

Hereafter, Q, R, and D are shown. The wavy line is a binding site.

1. Preparation of Resist Solution

Components having the following composition were mixed and dissolved to prepare a resist solution for an undercoat layer.

<Composition of Resist Solution for Undercoat Layer>

Solvent: propylene glycol monomethyl ether acetate 19.20 parts Solvent: ethyl lactate 36.67 parts Alkali-soluble resin: 40% PGMEA solution of benzyl 30.51 parts methacrylate/methacrylic acid/2-hydroxyethyl methacrylate copolymer (molar ratio = 60/22/18, weight-average molecular weight of 15,000, number- average molecular weight of 9,000) Ethylenically unsaturated double bond-containing 12.20 parts compound: dipentaerythritol hexaacrylate Polymerization inhibitor: p-methoxyphenol 0.0061 parts  Fluorine-based surfactant: F-475, manufactured by DIC  0.83 parts Corporation Photopolymerization initiator: trihalomethyl triazine- 0.586 parts based photopolymerization initiator (TAZ-107 manufactured by Midori Kagaku Co., Ltd.)

2. Manufacture of Undercoat Layer-Attached Silicon Wafer Substrate

A 6-inch silicon wafer was heated in an oven at 200° C. for 30 minutes. Next, the resist solution was applied onto this silicon wafer such that the dry film thickness became 1.5 μm. Further, the resultant was further heated and dried in an oven at 220° C. for 1 hour to form an undercoat layer, thereby obtaining an undercoat layer-attached silicon wafer substrate.

3. Preparation of Coloring Composition

3-1. Preparation of Blue Pigment Dispersion

A blue pigment dispersion 1 was prepared in the following manner.

A mixed solution consisting of 13.0 parts of C. I. Pigment Blue 15:6 (blue pigment, average particle size of 55 nm), 5.0 parts of Disperbyk111 as a pigment dispersant, and 82.0 parts of PGMEA was mixed and dispersed for 3 hours by a beads mill (zirconia beads having a diameter of 0.3 mm) to prepare a pigment dispersion. Thereafter, the pigment dispersion was further subjected to a dispersion treatment under a pressure of 2000 kg/cm³ and at a flow rate of 500 g/min, by using a high-pressure dispersing machine equipped with a depressurizing mechanism, NANO-3000-10 (manufactured by Nihon B.E.E Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a blue pigment dispersion 1 (a dispersion of C. I. Pigment Blue 15:6, pigment concentration of 13%) used in the coloring compositions of Examples or Comparative Examples.

For the obtained blue pigment dispersion, the particle size of the pigment was measured using a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)), and as a result, was found to be 24 nm.

3-2. Preparation of Coloring Composition

The following respective components were mixed, dispersed, and dissolved to obtain the respective coloring compositions of Examples 1 to 58 and Comparative Examples 1 and 2.

Cyclohexanone 1.133 parts Alkali-soluble resin (J1 or J2 shown below: the 0.030 parts compound shown in Table 1) Solsperse 20000 (1% cyclohexane solution, 0.125 parts manufactured by The LubrizolCorporation) Photopolymerization initiator (the compound of 0.012 parts the following structure: thecompound described in the following table) Dye (the compound described in the following table) 0.040 parts in terms of a solid content Pigment dispersion described in the following table 0.615 parts (pigment concentration of13.0%) Dipentaerythritol hexaacrylate 0.070 parts Glycerol propoxylate (1% cyclohexane solution) 0.048 parts

PB15:6 C. I. Pigment Blue 15:6

PB15:3 C. I. Pigment Blue 15:3

PR254 C. I. Pigment Red 254

4. Manufacture of Color Filter Using Coloring Composition

<Pattern Formation Example 1 in which Photolithography Method is Applied>

Each of the coloring compositions of Examples and Comparative Examples, which had been prepared as above, was applied onto the undercoat layer of the undercoat layer-attached silicon wafer substrate obtained in the above section 2, thereby forming a coloring composition layer (coating film). Then, a heating treatment (pre-baking) was carried out for 120 seconds by using a hot plate at 100° C. such that the dry film thickness of the coating film became 0.6 μm.

Next, by using an i-ray stepper exposure device FPA-3000i5+ (manufactured by CANON Inc.), the wafer was exposed at a wavelength of 365 nm through an island pattern mask having a 1.0 μm×1.0 μm pattern, by varying the exposure dose in a range from 50 mJ/cm² to 1200 mJ/cm².

Subsequently, the silicon wafer substrate, which had been irradiated with light and had a coating film formed thereon, was loaded onto a horizontal spin table of a spin shower developing machine (Model DW-30, manufactured by Chemitronics Co., Ltd.), and subjected to paddle development at 23° C. for 60 seconds by using CD-2000 (manufactured by FUJIFILM Electronic Materials CO., LTD.), thereby forming a colored pattern on the silicon wafer substrate.

The silicon wafer on which the colored pattern had been formed was fixed onto the horizontal spin table by a vacuum chuck method, and the silicon wafer substrate was rotated at a rotation frequency of 50 r.p.m. by using a rotation device. In this state, from the position above the rotation center, pure water was supplied onto the wafer from a spray nozzle in the form of shower so as to perform rinsing treatment, and then the wafer was spray-dried.

In the manner described above, a color filter having the colored pattern formed of the coloring compositions of Examples or Comparative Examples were manufactured.

Thereafter, the size of the colored pattern was measured by using a length measuring SEM “S-9260A” (manufactured by Hitachi, Ltd.). An exposure dose at which the pattern size became 1.0 μm was determined as an optimal exposure dose.

5. Evaluation of Performance

5-1. Pattern Deficit

100 colored patterns were observed, and the number of patterns with deficit was counted. The larger the number is, the worse the pattern deficit is. The results are shown in the following table.

5-2. Pattern Linearity

100 patterns were observed with a length measuring SEM to evaluate the pattern linearity

A: It has a rectangular shape and the side of the pattern is linear.

B: It has a rectangular shape and the side of the pattern is slightly distorted linear, but it was at a level such that there was no problem in practical use.

C: It is rounded and the side of the pattern is not smooth, and it was at a level such that there was a problem in practical use.

5-3. Evaluation of Color Migration

The absorbance of the colored pattern in each of the color filters was measured by MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.) (Absorbance A).

A CT-2000L solution (a transparent undercoating agent, manufactured by FUJIFILM Electronics Materials Co., Ltd.) was applied onto the surface, on which the colored pattern of the color filter had been formed, such that the dried film thickness became 1 μm, and dried to form a transparent film, and the film was subjected to a heating treatment at 280° C. for 5 minutes.

After the completion of heating, the absorbance of the transparent film adjacent to the colored pattern was measured by MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.) (Absorbance B).

The ratio [%] of the absorbance A value of the colored pattern which had been measured before heating to the absorbance B value of the obtained transparent film was calculated [the following (Equation A)]. The ratio was used as an index for evaluating the color migration to adjacent pixels. Color migration (%)=Absorbance B/Absorbance A×100  (Equation A)

5-4. Heat Resistance

The glass substrate on which the coloring composition obtained above had been applied was loaded onto a hot plate at 200° C. such that it came into contact with the substrate surface, and was heated for 1 hour. Then, the color difference (ΔE*ab value) before and after the heating was measured using a colorimeter MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.), and used as an index for evaluating the heat fastness, and the index was evaluated in accordance with the following evaluation criteria. A small ΔE*ab value indicates good heat resistance. Incidentally, the ΔE*ab value is a value determined from the following color-difference formula according to CIE 1976 (L*, a*, b*) color space (New Edition of Color Science Handbook (1985) p. 266, edited by The Color Science Association of Japan). ΔE*ab={(ΔL*)2+(Δa*)2+(Δb*)2}½

TABLE 6 Dye (A) Photopolymerization Alkali-soluble Pattern Color oligomer Pigment (C) initiator (D) resin (F) Pattern deficit linearity Heat resistance migration Example 1 S-1 PB15:6 I-1 J1 4 B 4.3 5 Example 2 S-1 PB15:3 I-1 J1 4 B 4.3 5 Example 3 S-2 PB15:6 I-1 J1 5 B 4.2 4 Example 4 S-2 PB15:3 I-1 J1 5 B 4.2 4 Example 5 S-3 PB15:6 I-1 J1 1 A 3.3 3 Example 6 S-4 PB15:6 I-1 J1 3 B 4.3 5 Example 7 S-5 PB15:6 I-1 J1 4 B 4.2 4 Example 8 S-6 PB15:6 I-1 J1 5 B 4.1 5 Example 9 S-7 PB15:6 I-1 J1 3 B 3.2 6 Example 10 S-8 PB15:6 I-1 J1 4 B 4.3 7 Example 11 S-9 PB15:6 I-1 J1 5 B 4.5 6 Example 12 S-10 PB15:6 I-1 J1 3 B 4.4 5 Example 13 S-11 PB15:6 I-1 J1 2 A 3.8 6 Example 14 S-12 PB15:6 I-1 J1 3 B 4.2 5 Example 15 S-13 PB15:6 I-1 J1 5 B 4.4 7 Example 16 S-14 PB15:6 I-1 J1 1 A 3.2 6 Example 17 S-15 PB15:6 I-1 J1 4 B 4.3 7 Example 18 S-16 PB15:6 I-1 J1 3 B 4.2 5 Example 19 S-17 PB15:6 I-1 J1 5 B 4.5 6 Example 20 S-18 PB15:6 I-1 J1 1 A 3.1 4 Example 21 S-19 PB15:6 I-1 J1 4 B 4.3 5 Example 22 S-20 PB15:6 I-1 J1 3 B 4.5 6 Example 23 S-21 PB15:6 I-1 J1 1 A 3.2 7 Example 24 S-22 PB15:6 I-1 J1 1 A 3.1 5 Example 25 S-23 PB15:6 I-1 J1 3 B 4.6 4 Example 26 S-24 PB15:6 I-1 J1 4 B 4.5 5 Example 27 S-25 PB15:6 I-1 J1 3 B 4.4 6 Example 28 S-26 PB15:6 I-1 J1 0 A 1.9 5 Example 29 S-27 PB15:6 I-1 J1 3 B 4.3 4 Example 30 S-28 PB15:6 I-1 J1 2 B 4.2 5 Example 31 S-29 PB15:6 I-1 J1 5 B 4.4 6 Example 32 S-30 PB15:6 I-1 J1 0 A 3.4 5 Example 33 S-31 PB15:6 I-1 J1 6 B 4.5 4 Example 34 S-32 PB15:6 I-1 J1 4 B 4.5 6 Example 35 S-33 PB15:6 I-1 J1 6 B 4.3 5 Example 36 S-34 PB15:6 I-1 J1 1 A 2.9 4 Example 37 S-35 PB15:6 I-2 J1 3 B 3.2 5 Example 38 S-36 PB15:6 I-3 J1 2 A 2.8 2 Example 39 S-37 PB15:6 I-4 J1 2 A 2.4 3 Example 40 S-38 PB15:6 I-5 J1 1 A 2.3 2 Example 41 S-39 PB15:6 I-6 J1 2 A 2.4 3 Example 42 S-40 PB15:6 I-7 J1 2 A 2.3 2 Example 43 S-41 PB15:6 I-8 J1 2 A 2.3 1 Example 44 S-42 PB15:6 I-1/I-2 J1 1 A 2.2 2 Example 45 S-43 PB15:6 I-1/I-2 J1 2 A 2.2 2 Example 46 S-44 PB15:6 I-1/I-2 J1 1 A 2.4 2 Example 47 S-45 PB15:6 I-1 J1/J2 2 A 1.9 1 Example 48 S-46 PB15:6 I-1 J1/J2 1 A 1.8 2 Example 49 S-47 PB15:6 I-1 J1/J2 2 A 1.8 3 Example 50 S-48 PB15:6 I-1 J1 2 A 1.9 2 Example 51 S-49 PB15:6 I-1 J2 2 A 2 2 Example 52 S-50 PR254 I-1 J1 4 A 2.1 4 Example 53 S-51 PB15:6 I-1 J1 0 A 2.2 2 Example 54 S-52 PB15:6 I-1 J1 0 A 1.5 1 Example 55 S-53 PB15:6 I-1 J1 1 A 2.3 1 Example 56 S-54 PB15:6 I-1 J1 2 A 2.2 1 Example 57 S-51/S-52 PB15:6 I-1 J1 0 A 1.8 1 Example 58 S/53/S-54 PB15:6 I-1 J1 1 A 2.2 1 Comparative polymer A PB15:6 I-1 J1 9 C 10.5 1 Example 1 Comparative monomer A PB15:6 I-1 J1 22 C 5.5 33 Example 2

It could be seen that the developing liquid resistance and the peeling solution resistance were excellent in the case where color filters were manufactured by photoresists, using the coloring compositions of Examples 1 to 58, whereas those properties deteriorated with the compositions of Comparative Examples 1 and 2.

6. Pattern Formation Example in which Dry Etching Method is Applied

6-1. Preparation of Coloring Composition

The following respective components were mixed, dispersed, and dissolved to obtain the respective coloring compositions of Examples 59 to 89, and Comparative Examples 3 and 4.

Cyclohexanone 1.133 parts Photopolymerization initiator (the compound of the 0.012 parts following structure: the compound described in Table 3) Dye (the compound described in the following table) 0.040 parts in terms of a solid content Pigment dispersion described in the following table 0.615 parts (pigment concentration of 13.0%) Polymerizable compound (EHPE-3150 (1,2-epoxy-4-(2- 0.070 parts oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)- 1-butanol, manufactured by Daicel Corporation)) Glycerol propoxylate (1% cyclohexane solution) 0.048 parts

7. Performance Evaluation

7-1. Resistance to Alkaline Developing Liquid (Resistance to Developing Liquid)

The coloring composition was applied onto a glass substrate, using a spin coater such that the film thickness became 0.6 μm, and subjected to a heating treatment (pre-baking) using a hot plate at 100° C. for 120 seconds. Subsequently, a heating treatment (post-baking) was carried out by using a hot plate at 220° C. for 300 seconds to prepare a cured film.

The transmittance of the color filter thus obtained was measured at a wavelength region of 300 nm to 800 nm by a spectrophotometer (reference: glass substrate), which is an Ultraviolet-Visible-Near infrared spectrophotometer, UV3600 (manufactured by SHIMADZU Corporation). In addition, differential interference images were observed through reflective observation (50× magnifications) by using an optical microscope, BX60, manufactured by OLYMPUS Corporation.

Subsequently, the color filter was immersed in an alkaline developing liquid, FHD-5 (manufactured by FUJIFILM Electronic Materials CO., LTD.) for 5 minutes, dried, and then subjected to spectrometry again. Thus, a variance in the transmittance before and after immersion in an alkaline developing liquid was determined from the following Equation (1), and evaluated according to the following criteria. Variance in the transmittance before and after immersion in an alkaline developing liquid=|T0−T1|  (1)

T0: The transmittance of the color filter before immersion in an alkaline developing liquid

T1: The transmittance of the color filter after immersion in an alkaline developing liquid

AA: Good. A case where the variance in the transmittance before and after immersion in an alkaline developing liquid is less than 2% in the entire region in a range from 300 nm to 800 nm.

A: Slightly good. A case where the variance in the transmittance before and after immersion in an alkaline developing liquid is 2% or more and less than 5% in the entire region in a range from 300 nm to 800 nm.

B: Sufficient. A case where the variance in the transmittance before and after immersion in an alkaline developing liquid is 5% or more and less than 10% in the entire region in a range from 300 nm to 800 nm.

C: Insufficient. A case where the variance in the transmittance before and after immersion in an alkaline developing liquid is 10% or more in the entire region in a range from 300 nm to 800 nm.

7-2. Resistance to Peeling Solution

Then, a positive-type photoresist “FHi622BC” (manufactured by FUJIFILM Electronic Materials CO., LTD.) was applied onto the colored film manufactured in the section 7-1, and subjected to pre-baking to form a photoresist layer having a film thickness of 0.8 μm. Then, the photoresist layer was subjected to pattern exposure using an i-ray stepper (manufactured by CANON Inc.) in an exposure dose of 350 mJ/cm² and then to a heating treatment for 1 minute at temperature at which the temperature of the photoresist layer or ambient temperature reached 90° C. Thereafter, a peeling treatment was carried out using a photoresist peeling solution “MS230C” (manufactured by FUJIFILM Electronic Materials CO., LTD.) for 120 seconds to remove the resist pattern, and then cleaning with pure water and spin drying were carried out. Thereafter, dehydration and baking treatments at 100° C. for 2 minutes were carried out.

The obtained colored film was subjected to spectrometry and a variance in the transmittance before and after immersion in a photoresist peeling solution was determined from the following Equation (2), and evaluated according to the following criteria. Variance in the transmittance before and after immersion in a photoresist peeling solution=|T0−T2|  (2)

T0: The transmittance of the color filter before immersion in a photoresist developing liquid

T2: The transmittance of the color filter after immersion in a photoresist developing liquid

AA: Good. A case where the variance in the transmittance before and after immersion in a photoresist developing liquid is less than 2% in the entire region in a range from 300 nm to 800 nm.

A: Slightly good. A case where the variance in the transmittance before and after immersion in a photoresist developing liquid is 2% or more and less than 5% in the entire region in a range from 300 nm to 800 nm. 800 nm.

B: Sufficient. A case where the variance in the transmittance before and after immersion in a photoresist developing liquid is 5% or more and less than 10% in the entire region in a range from 300 nm to 800 nm.

C: Insufficient. A case where the variance in the transmittance before and after immersion in a photoresist developing liquid is 10% or more in the entire region in a range from 300 nm to 800 nm.

TABLE 7 Dye Resistance to Resistance to Example oligomer Pigment developing liquid peeling solution Example 59 S-24 PB15:6 A A Example 60 S-25 PB15:6 A A Example 61 S-26 PB15:6 AA AA Example 62 S-27 PB15:6 A A Example 63 S-28 PB15:6 A A Example 64 S-29 PB15:6 A A Example 65 S-30 PB15:6 A A Example 66 S-31 PB15:6 A A Example 67 S-32 PB15:6 A A Example 68 S-33 PB15:6 A A Example 69 S-34 PB15:6 A A Example 70 S-35 PB15:6 A A Example 71 S-36 PB15:6 AA AA Example 72 S-37 PB15:6 AA A Example 73 S-38 PB15:6 AA AA Example 74 S-39 PB15:6 A A Example 75 S-40 PB15:6 AA A Example 76 S-41 PB15:6 A A Example 77 S-42 PB15:6 AA A Example 78 S-43 PB15:6 A A Example 79 S-44 PB15:6 AA AA Example 80 S-45 PB15:6 AA A Example 81 S-46 PB15:6 AA AA Example 82 S-47 PB15:6 AA A Example 83 S-48 PB15:6 AA AA Example 84 S-49 PB15:6 A A Example 85 S-50 PB15:6 A A Example 86 S-51 PB15:6 AA AA Example 87 S-52 PB15:6 AA AA Example 88 S-53 PB15:6 AA AA Example 89 S-54 PB15:6 AA AA Comparative Polymer A PB15:6 B C Example 3 Comparative Monomer PB15:6 C C Example 4 A

It could be seen that the developing liquid resistance and the peeling solution resistance were excellent in the case where color filters were manufactured by etching resists using the coloring compositions of Examples 59 to 89, whereas those properties deteriorated with the compositions of Comparative Examples 3 and 4.

8. Pattern Formation Example 2 in which Photolithography Method is Applied

8-1. Preparation of Coloring Composition

The following respective components were mixed, dispersed, and dissolved to obtain the coloring compositions of Examples 90 to 192.

-   -   Cyclohexanone: 17.12 parts     -   Alkali-soluble resin 1 (Copolymer of benzyl methacrylate (BzMA)         and methacrylic acid (MAA), 30% PGMEA solution): 1.23 parts     -   Alkali-soluble resin 2 (ACRYCURE-RD-F8 (manufactured by Nippon         Shokubai Co., Ltd.)): 0.23 parts     -   Photopolymerization initiator 1-2 (IRGACURE OXE-02): 0.975 parts     -   Cyclohexanone solution of dye (the compound described in the         following table) (solid content concentration 12.3%): 24.57         parts     -   Pigment dispersion (C. I. Pigment Blue 15:6 dispersion, PGMEA         solution, solid content concentration 12.8%): 51.40 parts     -   Polymerizable compound (dipentaerythritol hexaacrylate, NK Ester         A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.)):         1.96 parts     -   Polymerization inhibitor (p-methoxyphenol): 0.0007 parts     -   Fluorine-based surfactant (F475 manufactured by DIC Corporation,         1% PGMEA solution): 2.50 parts

8-2. Manufacture of Color Filter

The coloring composition prepared as above was applied onto the undercoat layer of the undercoat layer-attached silicon wafer substrate obtained in the above section 2, thereby forming a coloring composition layer (coating film). Then, a heating treatment (pre-baking) was carried out for 120 seconds by using a hot plate at 100° C. such that the dry film thickness of the coating film became 1 μm.

Next, by using an i-ray stepper exposure device FPA-3000i5+ (manufactured by CANON Inc.), the wafer was exposed at a wavelength of 365 nm through an island pattern mask having a 1.0 μm×1.0 μm pattern, by varying the exposure dose in a range from 50 mJ/cm² to 1200 mJ/cm².

Subsequently, the silicon wafer substrate, which had been irradiated with light and had a coating film formed thereon, was loaded onto a horizontal spin table of a spin shower developing machine (Model DW-30, manufactured by Chemitronics Co., Ltd.), and subjected to paddle development at 23° C. for 60 seconds by using CD-2000 (manufactured by FUJIFILM Electronic Materials CO., LTD.), thereby forming a colored pattern on the undercoat layer-attached silicon wafer substrate.

The silicon wafer having the colored pattern formed thereon was fixed onto the horizontal spin table by a vacuum chuck method, and the silicon wafer substrate was rotated at a silicon rotation frequency of 50 rpm by using a rotation device. In this state, from the position above the rotation center, pure water was supplied onto the wafer from a spray nozzle in the form of shower so as to perform a rinsing treatment, and then the wafer was spray-dried. Next, post-baking was carried out by using a hot plate at 200° C. for 300 seconds to obtain a colored pattern (cured film) having a film thickness of 1 μm on the silicon wafer substrate.

In the manner described above, a color filter having the colored pattern formed of the coloring compositions of Examples 90 to 192 were manufactured.

Thereafter, the size of the colored pattern was measured by using a length measuring SEM “S-9260A” (manufactured by Hitachi, Ltd.).

By using a colored pattern having an exposure dose at which the pattern size became 1.0 μm, the transmittance, the developability, and the decoloration were evaluated.

8-3. Calculation of C═C Value

The C═C value of a dye was calculated by dividing the number of polymerizable groups introduced into the dye with the molecular weight of the dye.

8-4. Transmittance at 450 nm and 550 nm

The transmittance of the color filter thus obtained was measured at a wavelength region of 300 nm to 800 nm by a spectrophotometer (reference: glass substrate), which is an Ultraviolet-Visible-Near infrared spectrophotometer, UV3600 (manufactured by SHIMADZU Corporation). Thereafter, the transmittance at 450 nm and 550 nm was calculated, and the transmittance at 450 nm and 550 nm was evaluated in accordance with the following criteria.

A: A case where the transmittance at 450 nm is 85% or more, and the transmittance at 550 nm is 5% or less

B: A case where the transmittance at 450 nm is 80% or more and less than 85%, and the transmittance at 550 nm is 5% or more and less than 10%

C: A case where the transmittance at 450 nm is 80% or less, and the transmittance at 550 nm is 10% or more

D: None of A to C

8-5. Developability

The manufactured color filter was cut using a glass cut, and the cross-section thereof was observed at a magnification of 15,000, using a scanning type electron microscope (S-4800, manufactured by Hitachi, Ltd.), and evaluated in accordance with the following evaluation criteria.

A: A pattern was formed without problem.

B: The pattern is slightly distorted linear, but it was at a level such that there was no problem in practical use.

C: The pattern is distorted or is not formed, and it was at a level such that there was a problem in practical use.

8-6. Decoloration

The coloring compositions of Examples 90 to 192 were applied onto a glass substrate, using a spin coater, such that the film thickness became 0.6 μm, and subjected to a heating treatment (pre-baking) by using a hot plate at 100° C. for 120 seconds. Subsequently, a heating treatment (post-baking) was carried out with a hot plate at 220° C. for 300 seconds to prepare a cured film.

The transmittance of the color filter thus obtained was measured at a wavelength region of 300 nm to 800 nm by a spectrophotometer (reference: glass substrate), which is an Ultraviolet-Visible-Near infrared spectrophotometer, UV3600 (manufactured by SHIMADZU Corporation). In addition, differential interference images were observed through reflective observation (50× magnifications) by using an optical microscope, BX60, manufactured by OLYMPUS Corporation.

Subsequently, the color filter was immersed in an alkaline developing liquid, FHD-5 (manufactured by FUJIFILM Electronic Materials CO., LTD.) for 5 minutes, dried, and then subjected to spectrometry again. Thus, a variance in the transmittance before and after immersion in an alkaline developing liquid was determined from the following Equation (1), and evaluated according to the following criteria. Variance in the transmittance before and after immersion in an alkaline developing liquid=|T0−T1|  (1)

T0: The transmittance of the color filter before immersion in an alkaline developing liquid

T1: The transmittance of the color filter after immersion in an alkaline developing liquid

AA: Good. A case where the variance in the transmittance before and after immersion in an alkaline developing liquid is 2% or more and less than 5% in the entire region in a range from 300 nm to 800 nm.

B: Sufficient. A case where the variance in the transmittance before and after immersion in an alkaline developing liquid is 5% or more and less than 10% in the entire region in a range from 300 nm to 800 nm.

C: Insufficient. A case where the variance in the transmittance before and after immersion in an alkaline developing liquid is 10% or more in the entire region in a range from 300 nm to 800 nm.

TABLE 8 Acid C = C Compound Molecular value value No. weight (mmol/g) (mmol/g) Developability Decoloration Transmittance Example 1 3841 0.52 0.26 A A A 90 Example 2 3996 0.25 0.50 A AA A 91 Example 3 3957 1.01 0.25 A A A 92 Example 4 4054 0.49 0.49 A AA A 93 Example 5 4028 0.50 0.50 A AA A 94 Example 6 3910 0.51 0.51 A AA A 95 Example 7 4438 0.23 0.00 A A A 96 Example 8 4510 0.44 0.00 A A A 97 Example 9 4496 0.44 0.00 A A A 98 Example 10 4626 0.86 0.00 A B A 99 Example 11 4665 0.21 0.21 A A A 100 Example 12 4723 0.42 0.21 A A A 101 Example 13 4710 0.42 0.21 A A A 102 Example 14 4651 0.43 0.22 A A A 103 Example 15 4588 0.44 0.22 A A A 104 Example 16 4743 0.21 0.42 A AA A 105 Example 17 4704 0.85 0.21 A A A 106 Example 18 4801 0.42 0.42 A AA A 107 Example 19 4775 0.42 0.42 A AA A 108 Example 20 4657 0.43 0.43 A AA A 109 Example 21 5434 0.18 0.00 B A A 110 Example 22 5506 0.36 0.00 A A A 111 Example 23 5492 0.36 0.00 A A A 112 Example 24 5622 0.71 0.00 A B A 113 Example 25 5661 0.18 0.18 B A A 114 Example 26 5719 0.35 0.17 A A A 115 Example 27 5706 0.35 0.18 A A A 116 Example 28 5647 0.35 0.18 A A A 117 Example 29 4888 1.02 0.20 A A A 118 Example 30 5043 0.79 0.40 A A A 119 Example 31 5004 1.40 0.20 A B A 120 Example 32 5101 0.98 0.39 A A A 121 Example 33 5075 0.99 0.39 A A A 122 Example 34 4957 1.01 0.40 A A A 123 Example 35 5834 0.86 0.00 A B A 124 Example 39 6061 0.82 0.16 A B A 125 Example 40 6119 0.98 0.16 A B A 126 Example 41 6106 0.98 0.16 A B A 127 Example 42 6047 0.99 0.17 A B A 128 Example 43 4501 0.44 0.22 A A A 129 Example 44 4656 0.21 0.43 A AA A 130 Example 45 4617 0.87 0.22 A A A 131 Example 46 4714 0.42 0.42 A AA A 132 Example 47 4688 0.43 0.43 A AA A 133 Example 48 4570 0.44 0.44 A AA A 134 Example 49 5318 0.19 0.00 B A A 135 Example 50 5390 0.37 0.00 A A A 136 Example 51 5376 0.37 0.00 A A A 137 Example 52 5506 0.73 0.00 A B A 138 Example 53 5545 0.18 0.18 B A A 139 Example 54 5603 0.36 0.18 A A A 140 Example 55 5590 0.36 0.18 A A A 141

TABLE 9 Acid C=C Compound Molecular value value No. weight (mmol/g) (mmol/g) Developability Decoloration Transmittance Example 56 5531 0.36 0.18 A A A 142 Example 57 4381 0.46 0.23 A A A 143 Example 58 4536 0.22 0.44 A AA A 144 Example 59 4497 0.89 0.22 A A A 145 Example 60 4594 0.44 0.44 A AA A 146 Example 61 4568 0.44 0.44 A AA A 147 Example 62 4450 0.45 0.45 A AA A 148 Example 63 5066 0.20 0.00 B A A 149 Example 64 5138 0.39 0.00 A A A 150 Example 65 5124 0.39 0.00 A A A 151 Example 66 5254 0.76 0.00 A B A 152 Example 67 5293 0.19 0.19 B A A 153 Example 68 5351 0.37 0.19 A A A 154 Example 69 5338 0.37 0.19 A A A 155 Example 70 5279 0.38 0.19 A A A 156 Example 71 1789 0.56 0.56 A AA A 157 Example 72 1847 1.08 0.54 A A A 158 Example 73 1834 1.09 0.55 A A A 159 Example 74 1775 1.13 0.56 A A A 160 Example 75 2504 0.80 0.00 A B A 161 Example 76 3919 0.51 0.26 A A A 162 Example 77 4074 0.25 0.49 A AA A 163 Example 78 4035 0.99 0.25 A A A 164 Example 79 4132 0.48 0.48 A AA A 165 Example 80 4106 0.49 0.49 A AA A 166 Example 81 3988 0.50 0.50 A AA A 167 Example 82 4542 0.22 0.00 A A A 168 Example 83 4614 0.43 0.00 A A A 169 Example 84 4600 0.43 0.00 A A A 170 Example 85 4730 0.85 0.00 A B A 171 Example 86 4769 0.21 0.21 A A A 172 Example 87 4827 0.41 0.21 A A A 173 Example 88 4814 0.42 0.21 A A A 174 Example 89 4755 0.42 0.21 A A A 175 Example 90 3952 0.51 0.25 A A A 176 Example 91 4107 0.24 0.49 A AA A 177 Example 92 4068 0.98 0.25 A A A 178 Example 93 4165 0.48 0.48 A AA A 179 Example 94 4139 0.48 0.48 A AA A 180 Example 95 4021 0.50 0.50 A AA A 181 Example 96 4494 0.22 0.00 A A A 182 Example 97 4566 0.44 0.00 A A A 183 Example 98 4552 0.44 0.00 A A A 184 Example 99 4682 0.85 0.00 A B A 185 Example 100 4721 0.21 0.21 A A A 186 Example 101 4779 0.42 0.21 A A A 187 Example 102 4766 0.42 0.21 A A A 188 Example 103 4707 0.42 0.21 A A A 189 Example S-3 1790 0.56 0.00 A B B 190 Example S-37 2569 0.39 0.00 A B B 191 Example S-51 3602 0.28 0.28 A A B 192

Color filters were manufactured with photoresists, using the coloring compositions of Examples 90 to 192, and it could be seen that the developability and the decoloration properties are excellent.

It could also be seen that the transmittance at 450 nm was low, and further, the transmittance at 550 nm was high. For the color filter for blue, it could be seen that since it is preferable that the transmittance at 450 nm is low, and further, the transmittance at 550 nm is high, the color filters of Examples 90 to 192 have particularly preferred spectrophotometric characteristics as a color filter for blue color. 

What is claimed is:
 1. A coloring composition comprising: a dye (A) represented by the following General Formula (I); and a polymerizable compound (B): (R)_(m)-Q-(D)_(n)  General Formula (I) wherein in General Formula (I), R represents a substituent, D represents a dye residue, m represents an integer of 2 to 6, n represents an integer of 2 to 8, and (m+n) represents an integer of 4 to 8, provided that a plurality of R's may be different from each other and at least one of m number of R's is an acid group; at least one other of m number of R's is a polymerizable group; and a plurality of D's may be different from each other; the dye residue D in General Formula (I) is constituted with a cationic site and a counter ion; the dye residue D in General Formula (I) is selected from the group consisting of a triarylmethane dye and a xanthene dye; the counter anion constituting the dye residue D in General Formula (I) is selected from the group consisting of a sulfonylimide anion, a bis(alkylsulfonyl)imide anion, and a tetraarylborate anion; and Q represents a linking group represented by any one of the following formulas (10) to (21):


2. The coloring composition according to claim 1, wherein D represents a dye residue derived from a compound represented by General Formula (J):

wherein R⁸¹, R⁸², R⁸³, and R⁸⁴ each independently represents a hydrogen atom or a monovalent substituent; R⁸⁵'s each independently represent a monovalent substituent, and m represents an integer of 0 to 5; and X⁻ represents a bis(alkylsulfonyl)imide anion.
 3. The coloring composition according to claim 1, wherein at least one member selected from the group consisting of the linking group Q and the dye residue D in General Formula (I) contains an acid group.
 4. The coloring composition according to claim 1, further comprising a pigment (C) other than the dye (A).
 5. The coloring composition according to claim 1, further comprising a photopolymerization initiator (D).
 6. The coloring composition according to claim 5, wherein the photopolymerization initiator (D) is an oxime compound.
 7. The coloring composition according to claim 1, which is used for forming a colored layer of a color filter.
 8. The coloring composition according to claim 1, wherein the dye represented by General Formula (I) is an organic solvent-soluble dye.
 9. The coloring composition according to claim 1, wherein the dye represented by General Formula (I) has a polymerizable group.
 10. The coloring composition according to claim 1, wherein the molecular weight of the dye represented by General Formula (I) is 2000 to
 6000. 11. A cured film obtained by curing the coloring composition according to claim
 1. 12. A color filter obtained by using the coloring composition according to claim
 1. 13. A solid-state imaging element comprising the color filter according to claim
 12. 14. An image display device comprising the color filter according to claim
 12. 15. A method for producing a color filter, comprising: applying the coloring composition according to claim 1 onto a support to form a coloring composition layer; patternwise exposing the coloring composition layer; and removing an unexposed area by development to form a colored pattern.
 16. A method for producing a color filter, comprising: applying the coloring composition according to claim 1 onto a support to form a coloring composition layer, and curing the coloring composition layer to form a colored layer; forming a photoresist layer on the colored layer; patterning the photoresist layer by exposure and development to obtain a resist pattern; and dry-etching the colored layer using the resist pattern as an etching mask to form a colored pattern.
 17. The coloring composition according to claim 1, wherein the molecular weight distribution of the dye (A) is from 1.00 to 1.20.
 18. The coloring composition according to claim 1, wherein at least one of m number of R's is a polymerizable group; and the polymerizable group is a group having an ethylenically unsaturated bond.
 19. The coloring composition according to claim 1, wherein Q represents a linking group represented by any one of the formulas (18) and (19).
 20. The coloring composition according to claim 1, wherein the counter anion constituting the dye residue Din General Formula (I) is selected from the group consisting of counter anions represented by the following formulas (a-10), (a-11), (a-12) and (a-13):


21. A coloring composition comprising: a dye (A) represented by the following General Formula (I); and a polymerizable compound (B): (R)_(m)-Q-(D)_(n)  General Formula (I) wherein in General Formula (I), R represents a substituent, D represents a dye residue which is a xanthene dye containing a bis(alkylsulfonyl) imide anion, m represents an integer of 2 to 6, n represents an integer of 2 to 8, and (m+n) represents an integer of 4 to 8, provided that a plurality of R's may be different from each other and at least one of m number of R's is an acid group; at least one other of m number of R's is a polymerizable group; and a plurality of D's may be different from each other; and Q represents a linking group represented by any one of the following formulas (10) to (21): 